Solvent extraction of oil from distillers dried grains and methods of using extraction products

ABSTRACT

A process for extraction of crude oil from distillers dried grain solubles and/or distillers dried grains and producing corn distillers meal that may be used as a livestock supplement is disclosed. For example, the corn distillers meal may be used as a crude protein supplement for use in a livestock feed diet or a poultry feed diet. The solvent extracted crude oil may be suitable for oleochemical processing for personal care and home care products, biodiesel production, and/or renewable diesel production from hydro-treating the extracted oil to make green diesel fuel.

RELATED APPLICATION

This application is a continuation of application Ser. No. 14/800,032,filed Jul. 15, 2015, now U.S. Pat. No. 9,523,062, issued Dec. 20, 2016,which in turn is a division of application Ser. No. 13/840,784, filedMar. 15, 2013, now U.S. Pat. No. 9,113,645, issued Aug. 25, 2015, whichin turn is a continuation-in-part of application Ser. No. 13/494,825,filed Jun. 12, 2012, now U.S. Pat. No. 9,351,505, issued May 31, 2016,which in turn is a continuation of application Ser. No. 12/442,934,filed Sep. 26, 2007, now U.S. Pat. No. 8,227,015, issued Jul. 24, 2012,which is a National Stage filing under 35 U.S.C. 37 of InternationalApplication No. PCT/US2007/079575, filed Sep. 26, 2007, which claims thebenefit of U.S. Provisional Application No. 60/847,188, filed Sep. 26,2006, each of which is hereby fully incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to the extraction of oil fromdistillers dried grains with solubles (DDGS) and/or distillers driedgrains (DDG) to produce distillers meal, methods of using the oilextracted from DDGS and/or DDG, and methods of using the distillersmeal. More particularly, described herein are methods for solventextraction of crude oil from DDGS and/or DDG to provide distillers mealhaving a desired nutrient content, animal feed supplements containingdistillers meal, methods of processing the extracted oil to provide oilsuitable for consumer use, biodiesel production, renewable dieselproduction from hydro-treating the extracted oil to make green dieselfuel, and/or oleochemical production.

BACKGROUND OF THE INVENTION

Ethanol can be produced using grains, such as corn, which are renewableresources. Presently, the majority of ethanol-producing biorefineries inthe United States are dry-grind corn biorefineries, and it is estimatedthat the present ethanol production capacity of such biorefineries runsinto the billions of gallons each year. Co-products of the ethanolbiorefining process are distillers dried grains and distillers driedgrains with solubles. Based on current production rates of ethanol fromdry-grind ethanol plants, approximately 40 million tons of DDGS areproduced in the United States annually.

Over the past few decades, achieving an ethanol product from grain-basedbiorefineries that is both commercial viable and truly renewable hasproven challenging. Two of the more significant hurdles are: 1) the costof grain-based ethanol production; and 2) the energy input to outputratio of grain-based ethanol production processes. As is easilyappreciated, these two problems are intertwined. Grain-based ethanolproduction has historically required significant and costly input offossil fuels (e.g., natural gas) to drive the biorefining process.Moreover, the amount of fossil fuel that has been historically requiredto drive grain-based ethanol production is costly, particularly so asthe cost of natural gas and other fossil fuels increases.

One of the ways by which the effective cost of grain-based ethanolproduction can be reduced is the sale of commercially valuableco-products of the biorefining process. DDGS are co-products ofgrain-based ethanol production processes that have recognized commercialvalue. In particular, DDGS are sold as a livestock feed supplement.Because it is primarily the starch of the grain that is consumed in theproduction of ethanol, the DDGS remaining after fermentation anddistillation contain nutritionally valuable fiber, protein and fat.Relative to raw grain, DDGS may even be considered a superior feed, asthey contain concentrated amounts of fiber, protein and fat, togetherwith a significantly reduced amount of starch. In addition, DDGS areconsiderably less expensive than some feeds of comparable nutritionalvalue.

SUMMARY OF THE INVENTION BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a flow-chart representation of the process by whichcrude oil is extracted from DDGS and refined into biodiesel andglycerine.

FIG. 2 provides a flow-chart representation of the process by whichbiodiesel and glycerine are produced from oil extracted from DDGS.

FIGS. 3A-3D provide a flow-chart representation of the oleochemicalproduction processing using oil extracted from DDGS and/or DDG accordingto certain aspects of the present invention.

FIG. 4 provides a flow-chart representation of the renewable dieselproduction process using oil extracted from DDGS and/or DDG according tocertain aspects of the present invention.

DETAILED DESCRIPTION OF THE DRAWINGS

It will be readily understood that the methods and materials as they aregenerally described and illustrated in the figures herein could bearranged and designed in a wide variety of different configurations.Thus, the following more detailed description of various embodiments ofthe methods and materials provided herein is not intended to limit thescope of the claims, but merely provides representative examples ofvarious embodiments of the subject matter recited in the appendedclaims. For example, though DDGS are referenced herein with respect tothe methods and materials described, it is to be understood thatdistillers dried grains (DDG) could also be utilized instead of or inaddition to the DDGS. In particular, DDG retain significant oil content,and in embodiments of the processes and methods described herein DDG maybe used in place of DDGS or in combination with DDGS. Moreover, DDGretain valuable nutrient properties and distillers meal, resulting fromsolvent extraction of DDG according to the methods described herein, mayalso be utilized as an animal feed supplement. Also, while every ethanolplant is configured differently, each ethanol plants handles recyclestreams differently, including recycling different process streams ofsolubles to the distilled dried grains. Thus, the following description,while specific to DDGS, should also be understood to be applicable toDDG.

As is described herein, the commercial value of DDG and DDGS fromgrain-based ethanol production processes can be further enhanced. Inparticular, commercially valuable amounts of oil can be extracted fromthe DDG and DDGS using a solvent extraction process. The solventextracted oil can then be further processed to provide, for example,food grade oil, such as food grade corn oil where the DDG and DDGS arederived from an ethanol biorefinery that utilizes corn grain as biomass.Alternatively, the oil extracted from DDG and DDGS can be subjected to atransesterification process, sometimes in conjunction with anesterification process, to yield biodiesel and glycerine. Alternatively,the oil extracted from DDG and DDGS can be subjected to a hydro-treatingprocess to yield a renewable green diesel fuel.

Still alternatively, the oil extracted from DDG and DDGS can besubjected to other oleochemical processing, such as fat splitting (orhydrolysis) of the glycerides (e.g., triglyceride, diglyceride andmonoglyceride) into different oleochemical fractions to produce crudefatty acids and glycerine. After the splitting process, the crude fattyacids may be subjected to additional processing, such as distillation,fractionation, and other methods of separation to produce crude,distilled and fractionated fatty acids. Likewise, the crude glycerinemay be subjected to additional processing, such as adsorptive filtrationusing adsorptive materials, such as activated carbon, and distillationto produce refined glycerine. The fatty acids and/or glycerine may besubjected to further chemical and enzymatic reactions to yield desiredoleochemicals for personal care products and home care products.

In some aspects, the glycerine is subjected to esterification anddistillation processing to yield distilled esters of glycerol.

In some aspects, the crude fatty acids are subjected to esterificationreactions to yield fatty acid esters or fatty acid methyl esters,esterification and distillation processing to yield distilledfractionated fatty esters, and/or esterification and epoxidationprocessing to yield alkyl epoxy esters. In some aspects, the crude fattyacids are subjected to ethoxylation processing to yield fatty acidethoxylates. In some aspects, the crude fatty acids are subjected toconjugation processing to yield conjugated fatty acids. In some aspects,the crude fatty acids are subjected to hardening processing to yieldsaturated fatty acids. In some aspects, the crude fatty acids aresubjected to hardening processing and then hydrogenation processing toyield fatty alcohols.

In some aspects, the crude fatty acids are subjected to esterificationprocessing to yield fatty acid methyl esters or the extracted oil canundergo transesterification to yield fatty acid methyl esters. The fattyacid methyl esters may be subjected to hydrogenation to yield fattyalcohols, sulfonation processing to yield α-sulfo fatty acid esters,and/or amidation to yield fatty acid alkanolamides. In some aspects, thefatty alcohols derived from fatty acids or fatty acid methyl esters maythen be subjected to Guerbet reaction to yield Guerbet alcohols,chlorination to yield alkyl chlorides, ethoxylation to yield fattyalcohol ethoxylates, sulfation to yield fatty alcohol sulfates and/oresterification to yield esters. The fatty alcohol ethoxylates mayfurther under propoxylation to yield fatty alcohol alkoxylates,sulfation to yield fatty alcohol ether sulfates, phosphatization toyield fatty alcohol ether phosphates and/or sulfation to yield fattyalcohol sulfosuccinates. In some aspects, the crude fatty acids aresubjected to fractionation processing to yield C12, C14, C16 and/or C18fractionated fatty acids.

The distillers meal resulting from solvent extraction as describedherein is still suitable for use as an animal feed ingredient, such as,for example, a feed supplement or constituent for domestic pets,livestock (such as beef cattle, dairy cattle, equine, sheep and/orswine), aquaculture or poultry, including chickens, geese and/or turkey.Therefore, solvent extraction of DDG and DDGS according to the methodsdescribed herein may facilitate a reduction in the effective costs ofproducing ethanol from a grain-based biorefinery, as it allows forproduction of multiple, commercially-valuable products from DDG andDDGS.

In one embodiment, ethanol production, solvent extraction of DDGS, andrefining of the crude oil removed from the DDGS can occur in a singlefacility. For example, in such an embodiment, a grain-based ethanolbiorefinery may further include facilities for solvent extraction of theDDGS produced at the biorefinery. In another such embodiment, agrain-based ethanol biorefinery may further include facilities forsolvent extraction of the DDGS produced at the biorefinery andfacilities for processing the crude oil extracted from the DDGS toprovide food-grade oil suitable for consumer use. In yet anotherembodiment, a grain-based ethanol biorefinery may further includefacilities for solvent extraction of the DDGS produced at thebiorefinery and facilities for processing and refining the crude oilextracted from the DDGS to produce biodiesel and glycerin. Byintegrating these operations within a single facility, processefficiencies may be gained and costs of solvent extracting the DDGS andprocessing or refining the extracted oil may be reduced.

Solvent Extraction of Crude Oil from DDGS and/or DDG

Using solvent extraction processes, commercially significant amounts ofcrude plant oils can be isolated from DDGS, while maintaining the valueof DDGS as a feed supplement. In one embodiment, the DDGS used in asolvent extraction process as described herein are selected from DDGSgenerated in ethanol production processes that utilize corn, barley,rye, sorghum, or soybean grain. In another embodiment, the DDGS used ina solvent extraction process are corn DDGS generated from a dry-grindcorn ethanol biorefinery.

Solvent extraction processes suitable for extraction of crude oil fromDDGS include processes that utilize ethanol, hexane, iso-hexane,petroleum distillate, mixtures thereof, or one or more other suitablesolvents, as known in the art, for oil extraction of DDGS. One ofordinary skill in the art will appreciate that such solvents may becommercial grade or reagent grade solvents. In some aspects, solventextraction processes suitable for extraction of crude oil from DDGS orcrude corn oil form corn DDGS include processes that utilize suitablenon-polar solvents that have a high solvent power for lipids, arecommercially available, are acceptable regulatory-recognized solventsand/or can be readily removed from the resulting product by commonlyaccepted methods such as distillation, washing and/or evaporation.

In some aspects, suitable non-polar solvents comprise saturatedhydrocarbons, such as one or more C₅-C₇-alkanes, particularly n-pentane,n-hexane and n-heptane, as well as the structural isomers thereof (i.e.,isopentane, neopentane, isohexane, 2-methylpentane, 2,3-dimethylbutane,neohexane, isoheptane, 2-methylhexane, 2,2-dimethylpentane,2,3-dimethylpentane, 2,4-dimethylpentane, 3-ethylpentane, and2,2,3-trimethylbutane), petroleum ether, or mixtures thereof. In someaspects, suitable non-polar solvents or mixtures thereof have a boilingpoint in the range from about 36° C. to about 99° C. In some aspects,the non-polar solvents may be purified or commercial grade. For example,in some aspects, a suitable non-polar solvent includes commercial gradehexane, which one of ordinary skill in the art will appreciate comprisesa mixture of n-hexane, other isomers of hexane and small amounts ofother miscellaneous hydrocarbons (i.e., acetone, methyl ethyl ketone,dichloromethane, and trichloroethylene, aromatics such as toluene and/orother types of petroleum hydrocarbons).

In some aspects, suitable solvents comprise mixtures of solventscontaining alkanes or blends of polar and non-polar solvents that formazeotropes. For example, suitable blends of polar and non-polar solventsmay include hexane:ethanol or hexane:isopropanol. Such solvents may alsoinclude ketones such as acetone. In some aspects, the azeotropecomprises a blend of polar and non-polar solvents, such that the blendis a positive azeotrope, which has a boiling point at a lowertemperature than any other ratio of its constituents.

In one embodiment, the solvent extraction process utilizes a solvent,such as, for example, hexane that serves to remove oil from the DDGSwithout substantially altering the protein or fiber content of the DDGS.Oil extraction of the DDGS as described herein yields a distillers meal.In one embodiment, the solvent extraction process removes about 60% ormore, about 65% or more, about 70% or more, about 75% or more, about 80%or more, or about 90% or more of the oil present in the DDGS. In anotherembodiment, the solvent extraction process is a hexane extractionprocess that removes about 60% or more, about 65% or more, about 70% ormore, about 75% or more, about 80% or more, or about 90% or more of theoil present in the DDGS. In yet another embodiment, the solventextraction process is a hexane extraction process that removes about 75%or more, about 80% or more, or about 90% or more of the oil present incorn DDGS. In yet another embodiment, the solvent extraction process isan extraction process using a mixture of non-polar solvents having aboiling point range between about 36° C. to about 99° C. that removesabout 60% or more, about 65% or more, about 70% or more, about 75% ormore, about 80% or more, or about 90% or more of the oil present inDDGS, and in some aspects corn DDGS. In yet another embodiment, thesolvent extraction process is an extraction process using an azeotropeof a polar solvent and an alkane solvent that removes about 75% or more,about 80% or more, or about 90% or more of the oil present in DDGS, andin some aspects corn DDGS. In yet another embodiment, the solventextraction process is a hexane extraction process that removes about 60%or more, about 65% or more, about 70% or more, about 75% or more, about80% or more, or about 90% or more of the oil present in DDGS produced ata dry-grind corn ethanol biorefinery. Corn DDGS typically include about5% up to about 15% by weight oil content, and in one embodiment, thesolvent extraction process is a hexane extraction process that resultsin a corn distillers meal having a residual oil content of approximately2-3% by weight, in some other aspects approximately 0.25-5% by weight,in some other aspects approximately 1-4% by weight, and in still someother aspects approximately 0.25-3% by weight. In another embodiment,corn DDGS are subjected to a hexane extraction process that results in acorn distillers meal having a residual oil content of no more than 3.0%by weight, in some aspects no more than 2.5% by weight.

Where the DDGS are produced at a dry-grind corn ethanol biorefinery, aflow-chart representation of suitable hexane extraction process is shownin FIG. 1. In a typical dry-grind process for ethanol production fromcorn, the DDGS are a co-product derived from the corn mash after thestarch has been converted to ethanol and the ethanol has been removed bydistillation. The stillage is typically subjected to centrifugation,evaporation and drying to remove residual liquid content, resulting inDDGS. Methods of extracting crude corn oil from corn DDGS are discussedin Sing et. al., “Extraction of Oil From Corn Distillers Dried Grainswith Solubles”, Transactions of the ASAE 41 (6), 1775-1777 (1998), theteachings of which are incorporated by reference herein. In addition,solvent extraction technologies and equipment are available from, forexample, Crown Iron Works Company of Minneapolis, Minn., U.S.A.Moreover, technology directed to removal of the oil from vegetableparticles, removal of residual solvent from solvent extracted materials,and recovery of solvents used in solvent extraction processes aredescribed in, for example, U.S. Pat. No. 6,996,917, U.S. Pat. No.6,766,595, U.S. Pat. No. 6,732,454, and U.S. Pat. No. 6,509,051. Thesepatents are assigned to Crown Iron Works Company, and the teachings ofeach of these patents are incorporated by reference herein.

Referring again to FIG. 1, which illustrates an embodiment of a solventextraction process that may be applied to DDGS, as a first step, DDGSmeal is fed into an extractor. In some aspects, the DDGS meal mayoptionally be ground before being fed into an extractor to reduce theparticle size of the DDGS meal. In some aspects, the DDGS meal is groundsuch that about 80%, in some aspects about 85%, in some aspects about90%, in some aspects about 95%, in some aspects about 99%, and in someaspects about 100% of the DDGS meal has a particle size less than about1 millimeter. In some aspects about 90% of the ground DDGS meal has aparticle size less than about 1 millimeter to about 150 microns, in someaspects less than about 840 microns to about 150 microns, in someaspects less than about 710 microns to about 150 microns, in someaspects less than about 595 microns to about 150 microns, and in someother aspects less than about 525 microns to about 150 microns. In otheraspects, the DDGS meal is ground such that at least 95% of the DDGS mealhas a particle size less than about 1 millimeter to about 150 microns,in some aspects less than about 840 microns to about 150 microns, insome aspects less than about 710 microns to about 150 microns, in someaspects less than about 595 microns to about 150 microns, and in someother aspects less than about 525 microns to about 150 microns. In someother aspects, the DDGS meal is ground such that about 99% of the DDGSmeal has a particle size less than about 1 millimeter to about 150microns, in some aspects less than about 840 microns to about 150microns, in some aspects less than about 710 microns to about 150microns, in some aspects less than about 595 microns to about 150microns, and in some other aspects less than about 525 microns to about150 microns.

In the extractor, the DDGS meal is washed with solvent, and in oneembodiment, the DDGS meal is turned at least once in order to ensurethat all DDGS particles are contacted as equally as practicable withsolvent. After washing, the resulting mixture of oil and solvent, calledmiscella, is collected for separation of the extracted oil from thesolvent. During the extraction process, as the solvent washes over theDDGS flakes, the solvent not only brings oil into solution, but maycollect fine, solid DDGS particles. These “fines” are generallyundesirable impurities in the miscella, and in one embodiment, themiscella is discharged from the separator through a device thatseparates or scrubs the fines from the miscella as the miscella iscollected for separation of the oil from the solvent.

In order to separate the oil and the solvent contained in the miscella,the miscella may be subjected to a distillation step. In this step, themiscella can, for example, be processed through an evaporator, whichheats the miscella to a temperature that is high enough to causevaporization of the solvent, but is not sufficiently high to adverselyaffect or vaporize the extracted oil. The oil may be further stripped ofsolvent in an oil stripper to further reduce residual solvent levels. Asthe solvent evaporates, it may be collected, for example, in acondenser, and recycled for future use. Separation of the solvent fromthe miscella results in a stock of crude oil, which may be furtherprocessed to provide, for example, food grade oil for ultimatelyconsumer uses or an oil product suitable for use in a renewable dieselprocess by hydro-treating the oil to produce green diesel or atransesterification process that yields fatty acid methyl esters for usein biodiesel and/or for ultimate use in the production of oleochemicals,as well as glycerine which may be produced as a consequent of processingthe oil.

After extraction of the oil, the wet, de-oiled DDGS may be conveyed outof the extractor and subjected to a drying process that removes residualsolvent. Removal of residual solvent is important to production ofdistillers meal suitable for use as an animal feed ingredient. In oneembodiment, the wet meal can be conveyed in a vapor tight environment topreserve and collect solvent that transiently evaporates from the wetmeal as it is conveyed into the desolventizer. As the meal enters thedesolventizer, it may be heated to vaporize and remove the residualsolvent. In order to heat the meal, the desolventizer may include amechanism for distributing the meal over one or more trays, and the mealmay be heated directly, such as through direct contact with heated airor steam, or indirectly, such as by heating the tray carrying the meal,or both. The desolventizer may further include multiple different traysfor carrying the meal through different processing steps within thedesolventizer. In order to facilitate transfer of the meal from one trayto another, the trays carrying the meal may include openings betweentrays that allow the meal to pass from one tray to the next.

Where the desolventizer utilizes multiple process steps to removeresidual solvent from the wet, de-oiled DDGS to produce distillers meal,the wet, de-oiled DDGS may be loaded and transferred through varioustrays to facilitate heating and solvent removal in multiple processsteps. For example, in one embodiment, as the meal enters thedesolventizer, it may be loaded on a first group of heated trays wherethe meal is evenly distributed and solvent vapor is flashed from themeal. From this first set of trays, the meal may be transferred onto asecond group of trays, where it is again evenly distributed. The secondset of trays may be heated indirectly by steam. The trays may bedesigned to allow venting of the solvent from one tray to the next andthe meal contained in the second set of trays travels counter current tothe solvent vapors. A third tray or set of trays may be provided toallow direct steam injection into the meal, which works to stripremaining solvent. Where the desolventizer includes multiple trays andutilizes multiple desolventizing processes, the quantity of trays andtheir positions may be designed to allow maximum contact between vaporsand meal.

From the desolventizer, the meal may be conveyed to a dryer where themeal is dried of residual excess water and cooled to provide a finisheddistillers meal. As it is conveyed into the dryer, the meal may bedeposited into drying trays and it is warmed by heated air. As the mealis heated, residual water is vaporized. After drying, the meal may becooled using ambient air. The desolventized, dried and cooled distillersmeal may be stored, further processed, such as pelletizing to increasedensification, or prepared for sale or distribution.

In some aspects, at least about 80%, in some aspects about 85%, in someaspects about 90%, in some aspects about 95%, in some aspects about 99%,and in some aspects about 100% of the distillers meal has a particlesize less than about 1 millimeter. In some aspects about 90% of thedistillers meal has a particle size less than about 1 millimeter toabout 150 microns, in some aspects less than about 840 microns to about150 microns, in some aspects less than about 710 microns to about 150microns, in some aspects less than about 595 microns to about 150microns, and in some other aspects less than about 525 microns to about150 microns. In other aspects, about 95% of the distillers meal has aparticle size less than about 1 millimeter to about 150 microns, in someaspects less than about 840 microns to about 150 microns, in someaspects less than about 710 microns to about 150 microns, in someaspects less than about 595 microns to about 150 microns, and in someother aspects less than about 525 microns to about 150 microns. In someother aspects, about 99% of the distillers meal has a particle size lessthan about 1 millimeter to about 150 microns, in some aspects less thanabout 840 microns to about 150 microns, in some aspects less than about710 microns to about 150 microns, in some aspects less than about 595microns to about 150 microns, and in some other aspects less than about525 microns to about 150 microns.

In some aspects, the distillers meal has an average particle size ofabout 105 microns to about 625 microns, in some aspects about 150microns to about 600 microns, in some aspects about 175 microns to about575 microns, in some aspects about 200 microns to about 525 microns, andin some aspects about 250 microns to about 500 microns.

In some aspects, the distillers meal may comprise a residual level ofsolvent utilized in the solvent extraction process in an amount of about10 ppm to about 2000 ppm, in other aspects about 10 ppm to about 1000ppm, in other aspects about 10 ppm to about 500 ppm, and still in someother aspects about 10 ppm to about 100 ppm. In some aspects, a residuallevel of hexane solvent is present in the distillers meal in an amountof about 10 ppm to about 2000 ppm, in other aspects about 10 ppm toabout 1000 ppm, in other aspects about 10 ppm to about 500 ppm, in otheraspects about 10 ppm to about 100 ppm, and in still other aspects about100 ppm to about 500 ppm. In some aspects, a residual level of hexanesolvent is present in the corn distillers meal in an amount of about 10ppm to about 2000 ppm, in other aspects about 10 ppm to about 1000 ppm,in other aspects about 10 ppm to about 500 ppm, in other aspects about10 ppm to about 100 ppm, and in still other aspects about 100 ppm toabout 500 ppm.

In some aspects, the distillers meal may comprise a residual moisturecontent of about 3% to about 15%, in some aspects about 4% to about 13%,and still in other aspects about 7% to about 11%.

The biorefining and solvent extraction processes may be tailored toprovide extracted oil exhibiting specific qualities. For example, wherethe DDGS are corn DDGS and the solvent extraction process is a hexaneextraction process, the biorefining and solvent extraction process maybe controlled to provide an extracted crude corn oil exhibiting no morethan about 15% by weight free fatty acids, such as oleic acid, no morethan about 1% by weight crude protein, about 0.5% by weight totalnitrogen, 0.2% by weight ash, about 0.05% phosphorus, about 0.01% byweight potassium, about 0.005% sodium, or about 0.05% by weight sulfur,or any combination of one or more such qualities. In one suchembodiment, the crude corn oil includes no more than about 0.6%, 0.7%,0.8% or 0.9% by weight crude protein. In another such embodiment, thecrude corn oil contains no more than about 10%, 11%, 12%, 13%, 14%, or15% by weight free fatty acids. In another such embodiment, the crudecorn oil contains free fatty acids in an amount between about 1% toabout 15%, in some aspects between about 1% and about 14%, in someaspects between about 1% and about 13%, in some aspects between about 1%and about 12%, in some aspects between about 1% and about 11%, in someaspects between about 1% and about 10%, in some aspects between about 1%and about 9%, in some aspects about 1% and about 8%, in some aspectsabout 3% to about 15%, by weight of the crude corn oil, with otherranges and subranges of the foregoing ranges contemplated. In anothersuch embodiment, the crude corn oil contains no more than about 0.09%,0.1%, 0.2%, 0.25%, 0.3%, or 0.4% by weight total nitrogen. In yetanother such embodiment, the crude corn oil contains no more than about0.08%, 0.09%, 0.1%, or 0.15% by weight ash. In another such embodiment,the crude corn oil contains no more than about 0.02%, 0.03%, or 0.04% byweight phosphorus. In yet another such embodiment, the crude corn oilcontains no more than about 0.02%, 0.03%, or 0.04% by weight potassium.In yet another such embodiment, the crude corn oil contains no more thanabout 0.003% or 0.004% by weight sodium. In yet another such embodiment,the crude corn oil contains no more than about 0.02%, 0.03%, or 0.04% byweight sulfur.

It is contemplated that where the DDGS is corn DDGS and the solventextraction process utilizes other solvents or mixtures of solventscontaining alkanes, the biorefining and solvent extraction process maybe controlled to provide an extracted crude oil exhibiting no more thanabout 15% by weight free fatty acids, such as oleic acid, no more thanabout 1% by weight crude protein, 0.5% by weight total nitrogen, 0.2% byweight ash, 0.05% phosphorus, 0.01% by weight potassium, 0.005% sodium,or 0.05% by weight sulfur, or any combination of one or more suchqualities. In one such embodiment, the crude corn oil includes no morethan about 0.6%, 0.7%, 0.8% or 0.9% by weight crude protein. In anothersuch embodiment, the crude oil contains no more than about 10%, 11%,12%, 13%, 14%, or 15% by weight free fatty acids. In another suchembodiment, the crude corn oil contains free fatty acids in an amountbetween about 1% to about 15%, in some aspects between about 1% andabout 14%, in some aspects between about 1% and about 13%, in someaspects between about 1% and about 12%, in some aspects between about 1%and about 11%, in some aspects between about 1% and about 10%, in someaspects between about 1% and about 9%, in some aspects about 1% andabout 8%, in some aspects about 3% to about 15%, by weight of the crudecorn oil, with other ranges and subranges of the foregoing rangescontemplated. In another such embodiment, the crude corn oil contains nomore than about 0.09%, 0.1%, 0.2%, 0.25%, 0.3%, or 0.4% by weight totalnitrogen. In yet another such embodiment, the crude corn oil contains nomore than about 0.08%, 0.09%, 0.1%, or 0.15% by weight ash. In anothersuch embodiment, the crude corn oil contains no more than about 0.02%,0.03%, or 0.04% by weight phosphorus. In yet another such embodiment,the crude corn oil contains no more than about 0.01%, 0.02%, 0.03%, or0.04% by weight potassium. In yet another such embodiment, the crudecorn oil contains no more than about 0.003% or 0.004% by weight sodium.In yet another such embodiment, the crude corn oil contains no more thanabout 0.02%, 0.03%, or 0.04% by weight sulfur.

In some aspects, the crude oil extracted utilizing a solvent extractionprocess on DDGS comprises a residual level of solvent utilized in thesolvent extraction process in an amount of about 1 ppm to about 500 ppm,in other aspects about 10 ppm to about 400 ppm, in other aspects about 1ppm to about 100 ppm, and still in some other aspects about 10 ppm toabout 100 ppm. In some aspects, a residual level of solvent is presentin the crude corn oil extracted from corn DDGS, the residual level ofhexane present in the crude oil present in an amount of about 1 ppm toabout 500 ppm, in other aspects about 10 ppm to about 400 ppm, in otheraspects about 1 ppm to about 100 ppm, and still in some other aspectsabout 10 ppm to about 100 ppm. In some aspects, a residual level ofhexane solvent is present in the crude oil extracted from DDGS, theresidual level of hexane present in the crude oil present in an amountof about 1 ppm to about 500 ppm, in other aspects about 10 ppm to about400 ppm, in other aspects about 1 ppm to about 100 ppm, and still insome other aspects about 10 ppm to about 100 ppm. In some aspects, aresidual level of hexane solvent is present in the crude corn oilextracted from corn DDGS, the residual level of hexane present in thecrude oil present in an amount of about 1 ppm to about 500 ppm, in otheraspects about 10 ppm to about 400 ppm, in other aspects about 1 ppm toabout 100 ppm, and still in some other aspects about 10 ppm to about 100ppm.

In comparing the contents of corn stillage oil (CSO), which is corn oilextracted from the stillage of an ethanol process, to that of crude cornoil extracted utilizing a solvent extraction process on corn DDGS, thecontent of phosphorous and phosphorous containing compounds in CSO ismore than about 100 ppm, and in some instances more than about 105 ppm,which is higher than solvent extracted crude corn oil, which in someaspects can have phosphorous and phosphorous containing compounds in anamount of about 1 ppm to about 50 ppm. Without wishing to be bound bytheory, while corn contains some native phosphorus content, which isprimarily in the form of phospholipids or phosphatides, the majority ofphosphorous is contributed by chemical addition during the ethanolprocess. The chemical forms of phosphorous, including phosphates, have arelatively high degree of solubility in water. Thus, in the process ofrecovering CSO, it is expected the various phosphorous forms would bepartially washed out with the CSO, and some residual phosphorous contentwould remain in the CSO. Conversely, these same water solublephosphorous compounds are not easily extracted with non-polar solvents,such as hexane. Consequently, crude corn oil extracted by a solventextraction process from corn DDGS contain initial levels of phosphorousand phosphorous containing compounds in an amount of about 1 ppm toabout 50 ppm, in some other aspects about 1 ppm to about 20 ppm, in someother aspects about 1 ppm to about 10 ppm, and in still other aspectsabout 1 ppm to about 5 ppm.

In comparing the contents of CSO to that of crude corn oil extractedutilizing a solvent extraction process on corn DDGS, the content ofsulfur and sulfur containing compounds in CSO is more than about 30 ppm,and in some instances about 34 ppm, which is higher than solventextracted crude corn oil, which in some aspects can have sulfur andsulfur containing compounds in an amount of about 1 ppm to about 20 ppm.While corn contains some native sulfur content, primarily bound in theform of amino acids such as methionine, the majority of sulfur iscontributed by chemical addition during the ethanol process. Both theamino acid form and the chemical forms, such as sulfates and sulfites,have a relatively high degree of solubility in water. Thus, in theprocess of recovering CSO, it is expected the various sulfur forms wouldbe partially washed out with the CSO, and some residual sulfur contentwould remain in the CSO. Conversely these same water soluble sulfurcompounds would not be easily extracted with non-polar solvents, such ashexane. Consequently, crude corn oil extracted by a solvent extractionprocess from corn DDG contain initial levels of sulfur and sulfurcontaining compounds in an amount of about 1 ppm to about 20 ppm, insome aspects less than about 15 ppm, in some aspects less than about 12ppm, in some other aspects about 1 ppm to about 10 ppm, and in stillother aspects about 1 ppm to about 5 ppm.

The CSO recovery process in ethanol plants relies on the concept ofusing an emulsifier to emulsify some of the free oil in water in orderto help wash out additional oil from the stillage. An emulsion breakersuch as flocculent may be used to separate the lipid and aqueouscomponents into distinct phases in order to fully recover the CSO. Crudeoil solvent extracted from DDGS, including crude corn oil solventextracted from corn DDGS, have reduced contents of non-nativeemulsifiers and also flocculants (i.e., those used in the Nalcoprocess). In some aspects, the crude oil solvent extracted from DDGS,including crude corn oil solvent extracted from corn DDGS, aresubstantially free of non-native emulsifiers and also flocculants. Crudeoil solvent extracted from DDGS, including crude corn oil solventextracted from corn DDGS, may also have a reduced content of acidsand/or reaction products resulting from the classic method of decreasingpH to break an emulsion. In some aspects, crude oil solvent extractedfrom DDGS, including crude corn oil solvent extracted from corn DDGS, issubstantially free of acids and/or reaction products resulting from theclassic method of decreasing pH to break an emulsion. In some aspects,the distillers meal of the present invention has a reduced residualcontent of any chemicals used for enhanced recovery of oil from stillageincluding one or more emulsifiers and/or flocculants, which are solublein solvent and/or oil. In some aspects, a non-polar solvent extractionreduces residual levels of such chemicals to levels of about 50% lessthan DDGS, in some aspects about 75% less, and in some aspects about 90%less, than DDGS that has not been solvent extracted but has beensubjected to CSO recovery using such chemicals. During the CSO recoveryprocess, an emulsifier may be used to help enhance the removal of oilfrom spent grains, and a flocculent may be used to further help recoveroil from thin stillage after mechanical separation.

Distillers Meal

The distillers meal produced by a solvent extraction method as describedherein retain desired nutritional properties. The solvent extractionprocess applied to the DDGS may be chosen and tailored to provide adistillers meal that exhibits nutritional properties suitable for animalfeed applications. For example, in one embodiment, the DDGS aresubjected to a solvent extraction process that provides distillers mealthat retains substantially all the crude protein and fiber content ofthe DDGS prior to solvent extraction. In another embodiment, thedistillers meal is corn distillers meal that retains substantially allof the crude protein and fiber content of the DDGS prior to solventextraction. In yet another embodiment, distillers meal is corndistillers meal that retains substantially all of the crude protein andfiber content of the DDGS prior to solvent extraction and is the productof a hexane extraction process conducted on corn DDGS produced by adry-grind corn ethanol biorefinery.

For example, where the DDGS are corn DDGS and the solvent extractionprocess is a hexane extraction, the biorefining and solvent extractionprocesses may be controlled to provide corn distillers meal having thefollowing nutrient content by weight on a dry matter basis: about 28% toabout 35% crude protein; about 4% to about 6% total nitrogen; about 1%to about 5% crude fat; about 4% to about 6% ash; about 5% to about 7%crude fiber; about 11.5% to about 16.5% acid detergent fiber; about 25%to about 35% neutral detergent fiber; about 50% to about 55% nitrogenfree extract; about 75% to about 80% total digestible nutrients (“TDN”);or a combination of two or more of any of the forgoing nutritionalproperties. In another embodiment, where the DDGS are corn DDGS and thesolvent extraction process is a hexane extraction, the biorefining andsolvent extraction processes may be controlled to provide corndistillers meal exhibiting about 0.80 to about 0.85 Mcal/lb net energylactation (NE/Lactation), about 0.85 to about 0.89 Mcal/lb net energymaintenance (NE/maintenance), about 1200 to about 1250 kcal/lb ofmetabolizable energy, or about 0.55 to about 0.60 Mcal/lb of net energygain (NE/gain), or any combination of two or more such characteristics.

It is contemplated that where the DDGS are corn DDGS and the solventextraction process utilizes other solvents or mixtures of solventscontaining alkanes, the biorefining and solvent extraction process maybe controlled to provide corn distillers meal having the followingnutrient content by weight on a dry matter basis: about 28% to about 35%crude protein; about 4% to about 6% total nitrogen; about 1% to about 5%crude fat; about 4% to about 6% ash; about 5% to about 7% crude fiber;about 11.5% to about 16.5% acid detergent fiber; about 25% to about 35%neutral detergent fiber; about 50% to about 55% nitrogen free extract;about 75% to about 80% total digestible nutrients (“TDN”); or acombination of two or more of any of the forgoing nutritionalproperties. In another embodiment, where the DDGS are corn DDGS and thesolvent extraction process is a hexane extraction, the biorefining andsolvent extraction processes may be controlled to provide corndistillers meal exhibiting about 0.80 to about 0.85 Mcal/lb net energylactation (NE/Lactation), about 0.85 to about 0.89 Mcal/lb net energymaintenance (NE/maintenance), about 1200 to about 1250 kcal/lb ofmetabolizable energy, or about 0.55 to about 0.60 Mcal/lb of net energygain (NE/gain), or any combination of two or more such characteristics.

The distillers meal may be further processed, as desired, to provide adistillers meal product having desired characteristics, such as, forexample, a desired flowabilty or density. Moreover, the distillers mealmay be further processed to provide a product that is more easilypackaged and distributed as an ingredient in a feed. Even further, thedistillers meal may be processed to incorporate additional constituentsto increase the feeding palatability or nutritional quality. Forexample, in one embodiment, the distillers meal may be further processedto incorporate a salt or a syrup from another manufacturing process thatprovides additional protein content. In another embodiment, thedistillers meal may be pelleted to provide a feed material that is morereadily packaged for sale and transport and is more easily incorporatedinto or used as an animal feed. For instance, Example 2 provides adescription of an embodiment of corn distillers meal according to thedescription provided herein, as well as suitable process conditions forpelletizing the corn distillers meal described therein. Tables presentedin Example 2 set out the process conditions under which the corndistillers meal was pelletized, describe a selection of physicalproperties exhibited by the non-pelleted and the pelleted corndistillers meal, and highlight a selection of nutritional propertiesexhibited by the non-pelleted and the pelleted corn distillers meal.

In some aspects, the solvent extracted crude oil from DDGS enhances thenutritional profile of the distillers meal by increasing the percentageof protein and amino acids contained in the distillers meal. Forexample, conventional corn DDGS having a corn oil content of about 10%typically has a lysine content of about 0.75% by weight on a dry matterbasis. In comparison, corn distillers meal of the present invention thathas a residual corn oil content of about 2% has a lysine content ofabout 0.81% by weight on a dry matter basis. This increase in lysinecontent in the corn distillers meal, when compared to the ratio ofresidual fat, results in a lysine to residual fat ratio percentage (%lysine/% residual fat)*100 of about 7.5 for conventional corn DDGS, ascompared to a lysine to residual fat ratio of about 40.5 for corndistillers meal of the present invention.

In some aspects, the lysine content of corn distillers meal ranges fromabout 0.7% to about 1.0% for corn distillers meal having a residual fatcontent between about 0.5% to about 3.0%. As a result, the lysine toresidual fat ratio for corn distillers meal is between about 23.3 toabout 140 at a lysine content of about 0.7%, between about 26.7 andabout 160 at a lysine content of about 0.8%, between about 30 and about180 at a lysine content of about 0.9%, and between about 33.3 and about200 at a lysine content of about 1.0%. Thus, corn distillers meal of thepresent invention may have a lysine to residual fat ratio between about20 to about 200, in some aspects about 25 to about 180, in some aspectsabout 30 to about 160, and in some other aspects about 40 to about 140,with other ranges and subranges of the foregoing ranges contemplatedherein. In comparison to an ethanol plant employing the CSO recoverymethod, and assuming a high native lysine content of about 0.9% and aresidual fat content of about 4%, the lysine to residual fat ratio wouldat the very most be about 20.

When one or more of the specific fatty acids in the residual fatcomposition of the corn distillers meal are considered as opposed to thetotal residual fat, such as linoleic acid (C18:2) or oleic acid (C18:1),the ratios are further enhanced. For example, in the situation oflinoleic acid, which is about 45% to about 60% of the total fatty acidcontent, and for the sake of this example assumed to be 50%, the lysineto linoleic acid ratio in corn distillers meal is in the range of about46.6 to about 280 at a lysine content of about 0.7%, between about 53.4and about 320 at a lysine content of about 0.8%, between about 60 andabout 360 at a lysine content of about 0.9%, and between about 66.6 andabout 400 at a lysine content of about 1.0%. Thus, corn distillers mealof the present invention may have a lysine to residual linoleic acidratio between about 45 to about 400, in some aspects about 50 to about360, in some aspects about 60 to about 320, and in some other aspectsabout 80 to about 280, with other ranges and subranges of the foregoingranges contemplated herein. In comparison to an ethanol plant employingthe CSO recovery method, and assuming a high native lysine content ofabout 0.9% and a residual fat content of about 4%, the lysine toresidual linoleic acid ratio would at the very most be about 40.

When oleic acid is used as the specific fatty acid instead of the totalresidual fat or linoleic acid, the ratios are even further enhanced. Forexample, in the situation of oleic acid, which is about 20% to about 40%of the total fatty acid content, and for the sake of this exampleassumed to be 25%, the lysine to oleic acid ratio in corn distillersmeal is in the range of about 85 to about 560 at a lysine content ofabout 0.7%, between about 105 and about 640 at a lysine content of about0.8%, between about 120 and about 720 at a lysine content of about 0.9%,and between about 125 and about 800 at a lysine content of about 1.0%.Thus, corn distillers meal of the present invention may have a lysine toresidual oleic acid ratio between about 85 to about 800, in some aspectsabout 105 to about 720, in some aspects about 120 to about 640, and insome other aspects about 160 to about 560, with other ranges andsubranges of the foregoing ranges contemplated herein. In comparison toan ethanol plant employing the CSO recovery method, and assuming a highnative lysine content of about 0.9% and a residual fat content of about4%, the lysine to residual linoleic acid ratio would at the very most beabout 40.

Conventionally, the protein content percentage in meals, such as flours,grains and oilseeds, is defined as the total nitrogen times 6.25, forexample 1% total nitrogen equals 6.25% protein. In conventional DDGS,including corn DDGS, the ratio of total nitrogen to total free fattyacids is less than 25. In distillers meal of the present invention,including corn distillers meal, the ratio of total nitrogen to totalfree fatty acids is greater than 25 up to about 200, in some aspectsabout 35 to about 200, and still in other aspects about 50 to about 200.In some aspects of the present invention, the total free fatty acidcontent in solvent extracted oil is about 2% to about 10%, in someaspects about 3% to about 9%, and in some aspects about 5% to about 8%,and in some further aspects about 7% to about 8%. In comparison, thefatty free acid content resulting from the CSO recovery method would beinherently higher due to the hydrolytic splitting of the oil in thepresence of water required for the CSO recovery method. As such, a freefatty acid content of about 10% or even higher for the CSO recoverymethod is not unusual.

Crude oil that is solvent extracted from DDGS, including crude corn oilthat is solvent extracted from corn DDGS, may also be substantially freeof non-native emulsifiers and also flocculants (i.e., Nalco process).Crude oil solvent extracted from DDGS, including crude corn oil solventextracted from corn DDGS, are also substantially free of acids and/orreaction products resulting from the classic method of decreasing pH tobreak an emulsion. In comparison, the CSO recovery process in ethanolplants relies on the concept of using an emulsifier to emulsify some ofthe free oil in water in order to help wash out additional oil from thestillage.

Further Processing of the Crude, Extracted Oil

After extraction from the DDGS, the crude oil may be further processedas desired. For example, the crude oil may be filtered, degummed,neutralized, bleached and/or deodorized to provide a food grade oil forconsumer use. For example, in one embodiment, the crude oil may bedegummed, caustic refined, and subjected to a soap removal stepaccording to commercially available processes, such as water washing.Following these steps the oil may then be subjected to one or more claybleaching steps to achieve an oil of desired content and color. Whereone or more clay bleaching steps are used, the clay may be an acidactivated clay or a non-acid activated clay, a silica based product,other adsorptive filtration media and/or combinations thereof and mayinclude, by way of example, an acid activated clay or a non-acidactivated clay at 0.1%-1%, 1-5%, 2-4%, or 2-3%. In addition to or as analternative to clay bleaching, after the crude oil has been degummed,caustic refined and subjected to a soap removal step, a food grade oilof a desired color, very low free fatty acid content, improved flavorand improved stability may be achieved using a deodorization stepwhereby thermal decomposition of color bodies and removal of volatilecomponents takes place under high temperature and high vacuum. Suitableprocesses for degumming, caustic refining, and soap removal are alsodescribed herein in relation to the pretreatment steps for biodiesel andglycerine production from the crude oil. Degumming, neutralization,bleaching and/or deodorization are also accessible to those of skill inthe art and can be utilized as described herein to achieve a food gradeoil and industrial grade oils.

Alternatively, the crude oil extracted from DDGS may be used to producebiodiesel and glycerine. A flow-chart representation of a process forrefining biodiesel and glycerine from the crude extracted oil is shownin FIG. 2. There are several processes that may be used to producebiodiesel from oils and fats, including base catalyzedtransesterification, direct acid catalyzed transesterification and/oresterification, enzyme catalyzed transesterification and/oresterification, high pressure transesterification (i.e. Henkel process),and/or a combination of same for conversion of the oil to biodiesel.Biodiesel production technologies and equipment are commerciallyavailable from, for example, Crown Iron Works Company of Minneapolis,Minn., U.S.A., and from Lurgi AG of Frankfurt, Germany. To producebiodiesel and glycerine from the crude oil extracted from the DDGS, anacid catalyzed esterification or caustic neutralization, followed by atransesterification process may be used.

In one embodiment, of the refining process outlined in FIG. 2, the crudeextracted oil is crude corn oil, and before the crude corn oil issubjected to a transesterification process, it may be pretreated.Pretreatment of the crude corn oil may be carried out, for example, toremove gums included in the oil or to remove or neutralize free fattyacids. As part of a degumming process, an acid, such as phosphoric acid,may be added to the crude corn oil and the crude oil may be heated, forexample, using steam. In such a process, the acid and steam work tohydrate the gums so that the gums can be separated from the crude cornoil, such as by centrifugation or another suitable separation technique.

Free fatty acids in the crude corn oil are generally undesirable becausethey form soaps within the oil as they react with the base catalyst usedto drive the transesterification reaction. If the crude corn oil is alsopretreated with a degumming step, the addition of the strong baseintended to neutralize the free fatty acids may occur after addition ofthe acid in the degumming step. In this manner, the base added toneutralize the free fatty acids can also work to neutralize the acidused in the degumming step. The soap stock that results from degummingand neutralization of the crude corn oil may be separated from the cornoil using standard equipment, such as a centrifugal separator.Alternatively, the free fatty acids can be removed and acid esterifiedto form biodiesel, or combined with glycerine to form triglycerides,which are then transesterified to form biodiesel.

Treatment of the crude corn oil may also include one or more bleachingsteps, such as one or more heat bleaching or clay bleaching steps asdescribed above, to remove residual color or other impurities from thecorn oil.

Where pretreatment of the crude corn oil includes degumming andneutralization of free fatty acids, prior to a transesterificationprocess, the degummed and neutralized oil is typically washed prior totransesterification. Washing may include, for example, mixing thepretreated corn oil with warm wash water. After washing, the oil andwash water are separated, and the pretreated corn oil is dried, such asby a vacuum-dryer, to a desired water content.

In one embodiment, the pretreated corn oil can be subjected to atransesterification reaction to provide biodiesel and glycerine. Thetransesterification reaction is based on the chemical reaction oftriglycerides contained in the crude corn oil with an alcohol in thepresence of an alkaline catalyst. The alkaline catalyst used in thetransesterification reaction may be selected from several differentalkaline materials. Suitable catalysts are strong bases and include, forexample, NaOH (caustic soda), KOH (potash), and CH.sub.3NaO (sodiummethylate). The alcohol used in the transesterification reaction may beselected from, for example, methanol or ethanol.

As the transesterification reaction is carried out, the alcohol andcatalyst may be delivered into the corn oil in parallel, as separatereaction components, or the alcohol and catalyst can be delivered to thecrude corn oil as a mixture. When delivered as a mixture, the catalystmay be dissolved in the alcohol by any suitable means prior to chargingthe mixture into the corn oil. Alternatively, the catalyst may beprovided as a liquid and mixed with the alcohol, limiting the need fordissolution of the catalyst in the alcohol prior to mixing the alcoholand catalyst with the corn oil. Where the catalyst is mixed with thealcohol as a liquid, the catalyst may be added to the alcohol by, forexample, one or more metering pumps. In addition, because an alkalinecatalyst might be sensitive to water, the catalyst may be stored in apump tank protected with a nitrogen layer.

In carrying out the transesterification reaction, the alcohol, catalystand corn oil may be charged into a closed reaction vessel. The reactionsystem can be closed to the atmosphere to prevent loss of the alcoholused in the transesterification reaction. As the reaction components aremixed, the mixture may be kept just below the boiling point of thealcohol to speed the reaction time. In addition, an excess amount ofalcohol is typically used to ensure total conversion of the corn oiltriglycerides into the desired ester product. The transesterificationreaction produces a two-phase reaction product that includes anester-rich phase (crude biodiesel) and a glycerine-rich phase (crudeglycerine). The crude glycerine is much more dense than the crudebiodiesel and the two phases can be easily separated by gravityseparation or, if needed or desired, centrifugation.

In one embodiment, transesterification of the corn oil takes place inone or more mixer-settler units. In such units, the transesterificationreaction occurs in a mixer or reactor included in the mixer-settlerunits. The crude biodiesel and crude glycerine resulting from thetransesterification reaction form two distinct phases that can beseparated in the settlers. If two or more mixer-settler units are usedas the reaction vessels, the feedstock and the intermediate product,respectively, may flow successively through the two or moremixer-settler units. Each mixer-settler unit can be supplied with thedesired alcohol and catalyst in parallel. The reactors included in themixer-settler units can be multi-stage in design, comprising variousreaction chambers in order to achieve maximum conversion efficiency tothe ester product. The settlers allow phase separation to approach thelimit of solubility, which eases downstream purification of thebiodiesel and glycerine products.

At the transesterification stage, vapors vented from the reactionvessel, such as the one or more mixer-settlers, may be routed to acondenser where they are partly or completely condensed and returned tothe reaction process. The same may be done with the vessel used to storeor deliver the alcohol used in the transesterification reaction. Evenfurther, where the catalyst is provided in liquid form, it too may bestored and delivered from a storage vessel, and any vapors vented fromthe catalyst storage vessel may also be captured, partly or completelycondensed, and returned to the reaction process in liquid form.

Once the transesterification reaction is complete, two major productsexist: glycerine and biodiesel. The glycerine is included in the crudeglycerine phase and the biodiesel is incorporated in the crude biodieselphase. Each of these crude phases may include a substantial excess ofthe alcohol used in the reaction. Moreover, the crude reaction productsmay include other impurities such as excess catalyst, soaps and highboiling impurities. If desired, some of these impurities may be treatedor removed from the crude reaction products before the crude biodieseland the crude glycerine phases are separated. For example, a suitableacid may be added to and mixed with the reaction products to neutralizeexcess catalyst and further help break any emulsions. Additionally,excess alcohol may be removed from the crude reaction products usingstandard distillation equipment and techniques.

After the crude biodiesel and crude glycerine are separated, they aretypically subjected to further refining. For example, after separation,the crude biodiesel may contain residual alcohol, glycerine, smallamounts of catalyst, and soaps. This may be the case even if the crudereaction products are refined to remove or neutralize impurities priorto separation. If they have not already been refined to neutralizeexcess catalyst or remove excess alcohol, or if residual catalyst andexcess alcohol still remain in the separated reaction products, thecrude biodiesel and crude glycerine may be treated with a suitable acidto neutralize the residual catalyst and subjected to, for example, aflash evaporation process or distillation to remove the excess alcohol.

Even where steps are taken to neutralize residual catalyst and removeexcess alcohol, the refined biodiesel may still include water solubleimpurities. In order to remove such water-soluble substances, therefined biodiesel may be washed and dried. To avoid the formation ofemulsions during washing, the biodiesel may be pH adjusted, for example,by the addition of an acid to the biodiesel to be washed. Dilute HCl,such as a 3.7% strength HCl, is suitable for such an application and canbe prepared and added as necessary. The biodiesel wash process maysimply include gentle mixing of the biodiesel with warm water, whichwill work to remove residual, water soluble impurities as they are takenup in the aqueous phase.

If the biodiesel is processed through such a washing step, the refinedand washed biodiesel may contain excess water. Such excess water may beremoved, for example, by subjecting the biodiesel to a drying step. Thedrying step may include, for example, vacuum drying the biodiesel to adesired water content in a dryer circuit. The dried biodiesel, which isready for use, distribution or sale, is collected and stored. Though thebiodiesel is serviceable at this point, if desired, it can be subjectedto further distillation to remove any color bodies and other highermolecular weight impurities remaining to provide a colorless biodiesel.

The separated, crude glycerine phase may also be further refined afterseparation. In particular, the crude glycerine may be neutralized with asuitable acid, the excess alcohol may be removed by distillation orflash evaporation, and the crude glycerine may be dried to removeresidual water. Even if the crude reaction products of thetransesterification process are neutralized and the excess alcoholpresent in the crude reaction products is removed prior to separation,the separated, crude glycerine may still contain residual catalyst oralcohol. Where that is the case, the separated, crude glycerine may besubjected to additional neutralization, absorptive filtration, and/ordistillation steps to neutralize any residual catalyst and remove anyremaining alcohol. Once such neutralization, distillation and dryingsteps are complete, the crude product typically contains approximately80-88% pure glycerine. This crude glycerine can be further refined to apurity of 99% or higher, as is known in the art, such that the glycerineproduct is suitable for use in cosmetic or pharmaceutical applications.

In order to minimize loss of the alcohol used in the transesterificationreaction, all vessels which contain alcohol, whether in substantiallypure form or as part of a crude reaction product, may be connected to avent system to capture any alcohol vapors. Captured alcohol vapors maybe fed into a condensing system that recovers the alcohol and recyclesthe alcohol back into the refining process.

Still alternatively, the crude oil extracted from DDGS may be used toproduce other oleochemicals, particularly oleochemicals for the personalcare products and home care products industries. A flow-chartrepresentation of oleochemical processing of crude oil extracted fromDDGS is shown in FIGS. 3A-3D. There are several processes that may beused to produce various oleochemicals after the crude oil undergoes asplitting (or hydrolysis) process of the triglycerides into crude fattyacids and glycerol/glycerine, followed by additional processingincluding esterification, fractionation, distillation, hydrogenation,epoxidation, ethoxylation, conjugation, hardening, chlorination and/orsulfation. After the splitting process, additional processing may beutilized prior to such processes, including evaporation, purificationand/or bleaching to produce glycerol/glycerine and crude fatty acids.The crude fatty acids and/or glycerine can be subjected to furtherchemical and enzymatic reactions to produce desired oleochemicals forpersonal care products and home care products.

In some aspects, the glycerine is subjected to esterification anddistillation processing to yield distilled fatty esters of glycerine.

In some aspects, the crude fatty acids are subjected to esterificationprocessing to yield fatty acid esters, esterification and distillationprocessing to yield distilled fractionated fatty esters, and/oresterification and epoxidation processing to yield alkyl epoxy esters.In some aspects, the crude fatty acids are subjected to ethoxylationprocessing to yield fatty acid ethoxylates. In some aspects, the crudefatty acids are subjected to conjugation processing to yield conjugatedfatty acids. In some aspects, the crude fatty acids are subjected tohardening processing to yield saturated fatty acids. In some aspects,the crude fatty acids are subjected to hardening processing and thenhydrogenation processing to yield fatty alcohols. In some aspects, thecrude fatty acids are subjected to esterification processing to yieldfatty acids methyl esters and then hydrogenation to yield fattyalcohols. In some aspects, the fatty alcohols derived from fatty acidsmay then be subjected to Guerbet reaction to yield Guerbet alcohols,chlorination to yield alkyl chlorides, ethoxylation to yield fattyalcohol ethoxylates, sulfation to yield fatty alcohol sulfates and/oresterification to yield esters. The fatty alcohol ethoxylates mayfurther under propoxylation to yield fatty alcohol alkoxylates,sulfation to yield fatty alcohol ether sulfates, phosphatization toyield fatty alcohol ether phosphates and/or sulfation to yield fattyalcohol sulfosuccinates. In some aspects, the crude fatty acids aresubjected to fractionation processing to yield C12, C14, C16 and/or C18fractionated fatty acids, with the remaining fraction subjected toesterification and distillation to yield distilled fractionated fattyesters.

Examples of common personal care ingredients ultimately derived fromthese fatty acids according to aspects of the present invention mayinclude octyl stearate, glyceryl stearate, PEG distearate andstearalkonium chloride. Examples of materials used in producing homecare products ultimately derived from these fatty acids according toaspects of the present invention may include sulfonated methyl estersand stearyl alcohol.

Still alternatively, the crude oil extracted from DDGS may be used toproduce a green renewable diesel fuel. As illustrated in FIG. 4, thecrude oil extracted from DDGS may be subjected to a hydro-treatingprocess, which involves the hydrogenation of the double bonds of theside chains of the triglycerides in the crude oil extracted from DDGSand the removal of oxygen on the metal sites of the catalysts. Thehydro-treating of the crude oil extracted from DDGS leads to theproduction of C14-C20 hydrocarbons, which is a liquid mixture with theboiling point range of diesel.

In the hydro-treating process, crude oil extracted from DDGS is thefeedstock, which may be mixed with recycle hydrogen and/or make-uphydrogen before being provided at process pressure in a reactor systemcomprising one or more catalytic hydrodeoxygenation reactors. In someaspects, the reactor is a multi-stage adiabatic, catalytichydrodeoxygenation reactor. In the reactor, the crude oil extracted fromDDGS is saturated and completely deoxygenated to yield deoxygenatedhydrocarbon products. The primary deoxygenation reaction by-products arepropane, water and carbon dioxide, which along with other low molecularweight hydrocarbons may be separated from the deoxygenated product. Insome aspects, the deoxygenated product is processed in a second reactorpacked with a selective hydrocracking catalyst where both cracking oflarger molecules and hydroisomerization takes place. In some aspects,the deoxygenated product is mixed with additional hydrogen gas for thehydroisomerization process. The excess hydrogen and the isomerizedproduct may be separated in a conventional gas/liquid separator. Theresulting product then undergoes separation in a fractional distillationcolumn where the various products are produced, including green propaneand light ends, green naphtha product, and green diesel product. Thegreen diesel product may include a green jet product and a green dieselproduct. The hydro-treating process for producing green diesel operatesin mild conditions and integrates well within existing petroleumrefineries. In some aspects, the hydro-treating process can be conductedonsite at an ethanol facility.

Distillers Meal as an Animal Feed or Animal Feed Supplement

DDGS are often used as a feed supplement for livestock and poultry fedhigh grain content finishing diets. Before solvent extraction, DDGS mayhave approximately 30% by weight crude protein (“CP”) and 20% crudefiber (“CF”). Solvent extraction as described herein removes most of theoil from the DDGS so that such oil can be processed or refined toprovide additional products of commercial value. However, because mostof the oil present in DDGS is removed in producing distillers meal, theenergy potential of the distillers meal from the fat content is lowerthan that exhibited by the DDGS prior to solvent extraction. Despite thelower energy potential resulting from oil extraction, distillers meal asdescribed herein provides a high-quality, low-cost protein feed that canbe fed at higher inclusion rates for animals, such as domestic pets,livestock or poultry. In addition, as described herein, livestock feeddistillers meal exhibit desirable carcass traits, and the nutritionalproperties of distillers meal may provide a superior feed or feedsupplement.

In one embodiment, the distillers meal disclosed herein may be used tosupplement animal diets at a desired percentage of the total diet, on adry matter basis. In one embodiment, the distillers meal may be used asa CP supplements in livestock and poultry feed diets. In addition, thedistillers meal described herein may also be used as an animal feed orfeed supplement that provides desired amounts of carbohydrates, fiber ornon-protein nitrogen (NPN) containing compounds. The distillers meal canbe used at a percentage of the total feed that maximizes the nutritionalcomponents of the feed. The relative amount of distillers mealincorporated into an animal diet may depend on, for example, thespecies, sex, or agricultural use of the animal being fed. Additionally,the relative amount of distillers meal incorporated into a particulardiet may depend on the nutritional goals of the diet.

In one embodiment, distillers meal may be used to provide approximately50% to approximately 75% by weight, on a dry matter basis, of a totaldiet for use in an animal feed. In one such embodiment, the distillersmeal is corn distillers meal as described herein and is used to provideapproximately 50% to 55%, 50% to 60%, 50% to 65%, or 50% to 70% byweight, on a dry matter basis, of the total diet. In some aspects, thedistillers meal is substituted in an animal feed diet for soybean meal,corn, DDGS and/or other protein supplements in rations for such animal.In another such embodiment, the distillers meal is corn distillers mealas described herein and is used to provide approximately 50% to 55%, 55%to 60%, 55% to 70%, 60% to 65%, 60% to 70%, or 70% to 75% by weight, ona dry matter basis, of the total diet. In some aspects, the corndistillers meal is substituted in an animal feed diet for soybean meal,corn, DDGS and/or other protein supplements in rations for such animal.

In another embodiment, distillers meal as described herein may be usedto provide approximately 0 to 5%, approximately 5% to 10%, approximately5% to 15%, approximately 5% to 25%, approximately 5% to 30%,approximately 10% to 15%, approximately 15% to 20%, approximately 20% to25%, approximately 25% to 30%, approximately 30% to 35%, approximately35% to 40%, approximately 40% to 45%, or approximately 45% to 50% byweight, on a dry matter basis, of a total animal diet. In one suchembodiment, distillers meal as described herein is used as a CPsupplement in a cattle diet, and the distillers meal providesapproximately 5% to 20% by weight, on a dry matter basis, of the totaldiet. In yet another such embodiment, distillers meal as describedherein is used as a CP supplement in a cattle diet, and the distillersmeal provides approximately 5% to 15% by weight, on a dry matter basis,of the total diet. In still yet another such embodiment, distillers mealas described herein is used as a CP supplement in a cattle diet, and thedistillers meal provides approximately 10% to 15% by weight, on a drymatter basis, of the total diet. In yet another such embodiment,distillers meal as described herein is used as a CP supplement in acattle diet, and the distillers meal provides approximately 10% to 12%by weight, on a dry matter basis of the total diet. In another suchembodiment, distillers meal as described herein is used as a CPsupplement in a cattle diet, and the distillers meal providesapproximately 7% to 12% by weight, on a dry matter basis, of the totaldiet. In each of the preceding embodiments, where the distillers meal isfed to cattle, the distillers meal may be corn distillers meal asdescribed herein and the cattle may be finishing cattle.

In another embodiment, distillers meal as described herein may be usedin feeding dairy cattle. Where corn distillers meal is used as a dairycattle feed, it may be provided at, for examples, up to approximately30%, approximately 5% to 30%, approximately 5% to 25%, approximately 5%to 20%, approximately 5% to 15%, approximately 10% to 15%, approximately15% to 20%, approximately 15% to 25%, approximately 15% to 30%,approximately 10% to 20%, approximately 10% to 25%, approximately 20% to25%, or approximately 25% to 30% by weight, on a dry matter basis, ofthe total diet. In each of the exemplary embodiments, where thedistillers meal is fed to dairy cattle, the distillers meal may be corndistillers meal as described herein.

In another embodiment, distillers meal as described herein is used as afeed supplement for cattle to achieve a desired F/G ratio. As it is usedherein, the term “F/G ratio” refers to the ratio of pounds of feed perpound of daily gain. In one embodiment, distillers meal as describedherein is used as a cattle feed supplement to achieve an F/G ratio of4.5 or less after 4 weeks of feeding. In another embodiment, distillersmeal as described herein is used as a cattle feed supplement to achievean F/G ratio of 5.0 or less after 8 weeks of feeding. In yet anotherembodiment, distillers meal as described herein is used as a cattle feedsupplement to achieve an F/G ratio of 6.5 or less after 12 weeks offeeding. In yet another embodiment, distillers meal as described hereinis used as a cattle feed supplement to achieve an F/G ratio of 7.0 orless after 16 weeks of feeding. In yet another embodiment, distillersmeal as described herein is used as a cattle feed supplement to achievean F/G ratio of 6.5 or less through 18 weeks of feeding. In each of theembodiments described herein pertaining to use of distillers meal as afeed supplement in cattle to achieve a desired F/G ratio, the distillersmeal may be corn distillers meal, the cattle may be, for example,finishing cattle, and the corn distillers meal may provide, for example,approximately 5% to 15%, 5% to 10%, 7%-12%, or 10% to 12% by weight, ona dry matter basis, of the total diet. Alternatively, in each of theembodiments described herein pertaining to use of distillers meal as afeed supplement in cattle to achieve a desired F/G ratio, the distillersmeal may be corn distillers meal, the cattle may be, for example,finishing cattle, and the corn distillers meal may provide, for example,approximately 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% byweight, on a dry matter basis, of the total diet.

In yet another embodiment, distillers meal as described herein may beused as a feed supplement for cattle to achieve a desired average dailygain (ADG). In one embodiment, distillers meal as described herein isused as a cattle feed supplement to achieve an ADG of 4.0 lbs or greaterafter 4 weeks of feeding. In another embodiment, distillers meal asdescribed herein is used as a cattle feed supplement to achieve an ADGof 4.5 lbs or greater after 8 weeks of feeding. In yet anotherembodiment, distillers meal as described herein is used as a cattle feedsupplement to achieve an ADG of 3.5 lbs or greater after 12 weeks offeeding. In yet another embodiment, distillers meal as described hereinis used as a cattle feed supplement to achieve and maintain an ADG of3.5 lbs or greater through 16 weeks of feeding. In yet anotherembodiment, distillers meal as described herein is used as a cattle feedsupplement to achieve and maintain an ADG of 3.5 lbs or greater through18 weeks of feeding. In yet another embodiment, distillers meal asdescribed herein is used as a cattle feed supplement to achieve an ADGof 4.0 lbs or greater after 18 weeks of feeding. In each of theembodiments described herein pertaining to use of distillers meal as afeed supplement in cattle to achieve a desired ADG, the distillers mealmay be corn distillers meal, the cattle may be, for example, finishingcattle, and the corn distillers meal may provide, for example,approximately 5% to 15%, 5% to 10%, 7%-12%, or 10% to 12% by weight, ona dry matter basis, of the total diet. Alternatively, in each of theembodiments described herein pertaining to use of distillers meal as afeed supplement in cattle to achieve a desired ADG, the distillers mealmay be corn distillers meal, the cattle may be, for example, finishingcattle, and the corn distillers meal may provide, for example,approximately 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% byweight, on a dry matter basis, of the total diet.

The distillers meal may be provided in meal form or in pellet form orother forms useful for feeding livestock or poultry, as would berecognized in the art. The distillers meal may also be premixed withother desired ingredients of a livestock or poultry diet and providedfor use in a ready-to-feed form. In addition to distillers meal asdescribed herein, livestock and poultry diets as described herein mayfurther include, for example, desired percentages of other componentssuch as feed corn, corn meal, soybean meal, urea, hay, pre-preparedcattle feeds, protein supplements, mineral supplements, liquidsupplements and other feed components as known and used by those ofskill in the art. Other acceptable materials used in livestock andpoultry feed may include, for example, soybeans, soy hulls, soybeanprotein derivatives, wheat, wheat middling, wheat straw, alfalfa, sugarbeet tailings, sugar beet pulp, sugar beets, corn stalks, corn cobs,popcorn husks, sweet bran, silage, meat and bone meal, molasses, oats,oat straw, barley, barley straw, sunflower seeds and hulls, milo, andwild grass, cottonseed by-products, such as delinted whole cottonseed,fuzzy cottonseed, and by-products of other oil seeds.

In some aspects, the distillers meal as described herein is used as afeed supplement or formula feed for beef cattle, including the beefcattle classes of calves, cattle on pasture and/or feedlot cattle. Thedistillers meal may have a minimum percentage of crude protein in anamount of about 28%, in some aspects about 29%, in some aspects about30%, in some aspects about 31%, in some aspects about 32%, in someaspects about 33%, in some aspects about 34%, and in some aspects about35%; a maximum percentage of equivalent crude protein from non-proteinnitrogen of about 6%, in some aspects about 5%, and in some aspectsabout 4%; a minimum percentage of crude fat in an amount of about 0.25%,in some aspects about 0.5%, in some aspects about 1%, in some aspectsabout 2%, in some aspects about 3%, in some aspects about 4%, and insome aspects about 5%; a maximum percentage of crude fiber in an amountof about 7%, in some aspects about 6%, and in some aspects about 5%; aminimum percentage of calcium in an amount of about 0.06%, in someaspects about 0.07%, and in some aspects about 0.08%, and a maximumpercentage of calcium in an amount of about 0.2%, in some aspects about0.1%, in some aspects about 0.15%, in some aspects about 0.095%, and insome other aspects about 0.09%; a minimum percentage of phosphorous inan amount of about 0.7%, in some aspects about 0.75%, and in some otheraspects about 0.8%; and a minimum percentage of potassium in an amountof about 0.8%, in some aspects about 0.85%, in some aspects about 0.9%,in some aspects about 0.95%, and in some other aspects about 1.0%.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for dairy cattle, particularly veal milkreplacer and/or herd milk replacer. The distillers meal may have aminimum percentage of crude protein in an amount of about 28%, in someaspects about 29%, in some aspects about 30%, in some aspects about 31%,in some aspects about 32%, in some aspects about 33%, in some aspectsabout 34%, and in some aspects about 35%; a minimum percentage of crudefat in an amount of about 0.25%, in some aspects about 0.5%, in someaspects about 1%, in some aspects about 2%, in some aspects about 3%, insome aspects about 4%, and in some aspects about 5%; a maximumpercentage of crude fiber in an amount of about 7%, in some aspectsabout 6%, and in some aspects about 5%; a minimum percentage of calciumin an amount of about 0.06%, in some aspects about 0.07%, and in someaspects about 0.08%, and a maximum percentage of calcium in an amount ofabout 0.2%, in some aspects about 0.1%, in some aspects about 0.15%, insome aspects about 0.095%, and in some other aspects about 0.09%; and aminimum percentage of phosphorous in an amount of about 0.8%, in someaspects about 0.85%, in some aspects about 0.9%, in some aspects about0.95%, and in some other aspects about 1.0%.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for dairy cattle, particularly starter,growing heifers, bulls and dairy beef, lactating dairy cattle and/ornon-lactating dairy cattle. The distillers meal may have a minimumpercentage of crude protein in an amount of about 28%, in some aspectsabout 29%, in some aspects about 30%, in some aspects about 31%, in someaspects about 32%, in some aspects about 33%, in some aspects about 34%,and in some aspects about 35%; a maximum percentage of equivalent crudeprotein from non-protein nitrogen of about 6%, in some aspects about 5%,and in some aspects about 4%; a minimum percentage of crude fat in anamount of about 0.25%, in some aspects about 0.5%, in some aspects about1%, in some aspects about 2%, in some aspects about 3%, in some aspectsabout 4%, and in some aspects about 5%; a maximum percentage of crudefiber in an amount of about 7%, in some aspects about 6%, and in someaspects about 5%; a maximum percentage of acid detergent fiber in anamount of about 16.5%, in some aspects about 15.5%, in some aspectsabout 14.5%, in some aspects about 13.5%, in some aspects about 12.5%,and still in some other aspects about 11.5%; a minimum percentage ofcalcium in an amount of about 0.06%, in some aspects about 0.07%, and insome aspects about 0.08%, and a maximum percentage of calcium in anamount of about 0.2%, in some aspects about 0.1%, in some aspects about0.15%, in some aspects about 0.095%, and in some other aspects about0.09%; a minimum percentage of phosphorous in an amount of about 0.7%,in some aspects about 0.75%, and in some other aspects about 0.8%; and aminimum selenium in an amount below detection limits of about 2.25 ppm.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for equine, including foal, mare,breeding and/or maintenance equine. The distillers meal may have aminimum percentage of crude protein in an amount of about 28%, in someaspects about 29%, in some aspects about 30%, in some aspects about 31%,in some aspects about 32%, in some aspects about 33%, in some aspectsabout 34%, and in some aspects about 35%; a minimum percentage of crudefat in an amount of about 0.25%, in some aspects about 0.5%, in someaspects about 1%, in some aspects about 2%, in some aspects about 3%, insome aspects about 4%, and in some aspects about 5%; a maximumpercentage of crude fiber in an amount of about 7%, in some aspectsabout 6%, and in some aspects about 5%; a minimum percentage of calciumin an amount of about 0.06%, in some aspects about 0.07%, and in someaspects about 0.08%, and a maximum percentage of calcium in an amount ofabout 0.2%, in some aspects about 0.1%, in some aspects about 0.15%, insome aspects about 0.095%, and in some other aspects about 0.09%; aminimum percentage of phosphorous in an amount of about 0.7%, in someaspects about 0.75%, and in some other aspects about 0.8%; a minimumamount of copper of about 3 ppm, in some aspects about 4 ppm, in someaspects about 5 ppm, in some aspects about 6 ppm; a minimum selenium inan amount below detection limits of about 2.25 ppm; and a minimum zincof about 50 ppm, in some aspects about 55 ppm, in some aspects about 60ppm, in some aspects about 65 ppm, in some aspects about 70 ppm, and insome other aspects about 75 ppm.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for swine, including pre-starter,starter, grower, finisher, gilts, sows and adult boars, lactating giltsand/or lactating sows. The distillers meal may have a minimum percentageof crude protein in an amount of about 28%, in some aspects about 29%,in some aspects about 30%, in some aspects about 31%, in some aspectsabout 32%, in some aspects about 33%, in some aspects about 34%, and insome aspects about 35%; a minimum percentage of lysine in an amount ofabout 0.7%, in some aspects about 0.75%, in some aspects about 0.8%, insome aspects about 0.85%, in some aspects about 0.9%, in some aspectsabout 0.95%, and in some other aspects about 1.0%; a minimum percentageof crude fat in an amount of about 0.25%, in some aspects about 0.5%, insome aspects about 1%, in some aspects about 2%, in some aspects about3%, in some aspects about 4%, and in some aspects about 5%; a maximumpercentage of crude fiber in an amount of about 7%, in some aspectsabout 6%, and in some aspects about 5%; a minimum percentage of calciumin an amount of about 0.06%, in some aspects about 0.07%, and in someaspects about 0.08%, and a maximum percentage of calcium in an amount ofabout 0.2%, in some aspects about 0.1%, in some aspects about 0.15%, insome aspects about 0.095%, and in some other aspects about 0.09%; aminimum percentage of phosphorous in an amount of about 0.7%, in someaspects about 0.75%, and in some other aspects about 0.8%; a minimumselenium in an amount below detection limits of about 2.25 ppm; and aminimum zinc of about 50 ppm, in some aspects about 55 ppm, in someaspects about 60 ppm, in some aspects about 65 ppm, in some aspectsabout 70 ppm, and in some other aspects about 75 ppm.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for poultry, including layer chickens(starting/growing, finisher, laying and/or breeder), broiler chickens(starting/growing, finisher and/or breeder), broiler breeder chickens(starting/growing, finishing and/or laying) and/or turkeys(starting/growing, finisher, laying and/or breeder). The distillers mealmay have a minimum percentage of crude protein in an amount of about28%, in some aspects about 29%, in some aspects about 30%, in someaspects about 31%, in some aspects about 32%, in some aspects about 33%,in some aspects about 34%, and in some aspects about 35%; a minimumpercentage of lysine in an amount of about 0.7%, in some aspects about0.75%, in some aspects about 0.8%, in some aspects about 0.85%, in someaspects about 0.9%, in some aspects about 0.95%, and in some otheraspects about 1.0%; a minimum percentage of methionine of about 0.50%,in some aspects about 0.55%, in some aspects about 0.60%, in some otheraspects about 0.65%, and in some other aspects about 0.7%; a minimumpercentage of crude fat in an amount of about 0.25%, in some aspectsabout 0.5%, in some aspects about 1%, in some aspects about 2%, in someaspects about 3%, in some aspects about 4%, and in some aspects about5%; a maximum percentage of crude fiber in an amount of about 7%, insome aspects about 6%, and in some aspects about 5%; a minimumpercentage of calcium in an amount of about 0.06%, in some aspects about0.07%, and in some aspects about 0.08%, and a maximum percentage ofcalcium in an amount of about 0.2%, in some aspects about 0.1%, in someaspects about 0.15%, in some aspects about 0.095%, and in some otheraspects about 0.09%; and a minimum percentage of phosphorous in anamount of about 0.7%, in some aspects about 0.75%, and in some otheraspects about 0.8%.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for a goat, including starter, grower,finisher, breeder and/or lactating goats. The distillers meal may have aminimum percentage of crude protein in an amount of about 28%, in someaspects about 29%, in some aspects about 30%, in some aspects about 31%,in some aspects about 32%, in some aspects about 33%, in some aspectsabout 34%, and in some aspects about 35%; a maximum percentage ofequivalent crude protein from non-protein nitrogen of about 6%, in someaspects about 5%, and in some aspects about 4%; a minimum percentage ofcrude fat in an amount of about 0.25%, in some aspects about 0.5%, insome aspects about 1%, in some aspects about 2%, in some aspects about3%, in some aspects about 4%, and in some aspects about 5%; a maximumpercentage of crude fiber in an amount of about 7%, in some aspectsabout 6%, and in some aspects about 5%; a minimum percentage of calciumin an amount of about 0.06%, in some aspects about 0.07%, and in someaspects about 0.08%, and a maximum percentage of calcium in an amount ofabout 0.2%, in some aspects about 0.1%, in some aspects about 0.15%, insome aspects about 0.095%, and in some other aspects about 0.09%; aminimum percentage of phosphorous in an amount of about 0.7%, in someaspects about 0.75%, and in some other aspects about 0.8%; a minimumamount of copper of about 3 ppm, in some aspects about 4 ppm, in someaspects about 5 ppm, in some aspects about 6 ppm, and a maximum amountof copper of about 10 ppm, in some aspects about 9 ppm, in some aspectsabout 8 ppm, in some aspects about 7 ppm, and in some other aspectsabout 6 ppm; and a minimum selenium in an amount below detection limitsof about 2.25 ppm.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for sheep, including starter, grower,finisher, breeder and/or lactating sheep. The distillers meal may have aminimum percentage of crude protein in an amount of about 28%, in someaspects about 29%, in some aspects about 30%, in some aspects about 31%,in some aspects about 32%, in some aspects about 33%, in some aspectsabout 34%, and in some aspects about 35%; a maximum percentage ofequivalent crude protein from non-protein nitrogen of about 6%, in someaspects about 5%, and in some aspects about 4%; a minimum percentage ofcrude fat in an amount of about 0.25%, in some aspects about 0.5%, insome aspects about 1%, in some aspects about 2%, in some aspects about3%, in some aspects about 4%, and in some aspects about 5%; a maximumpercentage of crude fiber in an amount of about 7%, in some aspectsabout 6%, and in some aspects about 5%; a minimum percentage of calciumin an amount of about 0.06%, in some aspects about 0.07%, and in someaspects about 0.08%, and a maximum percentage of calcium in an amount ofabout 0.2%, in some aspects about 0.1%, in some aspects about 0.15%, insome aspects about 0.095%, and in some other aspects about 0.09%; aminimum percentage of phosphorous in an amount of about 0.7%, in someaspects about 0.75%, and in some other aspects about 0.8%; a minimumamount of copper of about 3 ppm, in some aspects about 4 ppm, in someaspects about 5 ppm, in some aspects about 6 ppm, and a maximum amountof copper of about 10 ppm, in some aspects about 9 ppm, in some aspectsabout 8 ppm, in some aspects about 7 ppm, and in some other aspectsabout 6 ppm; and a minimum selenium in an amount below detection limitsof about 2.25 ppm.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for ducks and/or geese, includingstarter, grower, finisher, breeder developer and/or breeder. Thedistillers meal may have a minimum percentage of crude protein in anamount of about 28%, in some aspects about 29%, in some aspects about30%, in some aspects about 31%, in some aspects about 32%, in someaspects about 33%, in some aspects about 34%, and in some aspects about35%; a minimum percentage of crude fat in an amount of about 0.25%, insome aspects about 0.5%, in some aspects about 1%, in some aspects about2%, in some aspects about 3%, in some aspects about 4%, and in someaspects about 5%; a maximum percentage of crude fiber in an amount ofabout 7%, in some aspects about 6%, and in some aspects about 5%; aminimum percentage of calcium in an amount of about 0.06%, in someaspects about 0.07%, and in some aspects about 0.08%, and a maximumpercentage of calcium in an amount of about 0.2%, in some aspects about0.1%, in some aspects about 0.15%, in some aspects about 0.095%, and insome other aspects about 0.09%; and a minimum percentage of phosphorousin an amount of about 0.7%, in some aspects about 0.75%, and in someother aspects about 0.8%.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for fish, including trout, catfish andother species other than trout or catfish. The distillers meal may havea minimum percentage of crude protein in an amount of about 28%, in someaspects about 29%, in some aspects about 30%, in some aspects about 31%,in some aspects about 32%, in some aspects about 33%, in some aspectsabout 34%, and in some aspects about 35%; a minimum percentage of crudefat in an amount of about 0.25%, in some aspects about 0.5%, in someaspects about 1%, in some aspects about 2%, in some aspects about 3%, insome aspects about 4%, and in some aspects about 5%; a maximumpercentage of crude fiber in an amount of about 7%, in some aspectsabout 6%, and in some aspects about 5%; and a minimum percentage ofphosphorous in an amount of about 0.7%, in some aspects about 0.75%, andin some other aspects about 0.8%.

In some aspects, the distillers meal as described herein is used as afeed supplement or feed formula for rabbit, including grower and/orbreeder. The distillers meal may have a minimum percentage of crudeprotein in an amount of about 28%, in some aspects about 29%, in someaspects about 30%, in some aspects about 31%, in some aspects about 32%,in some aspects about 33%, in some aspects about 34%, and in someaspects about 35%; a minimum percentage of crude fat in an amount ofabout 0.25%, in some aspects about 0.5%, in some aspects about 1%, insome aspects about 2%, in some aspects about 3%, in some aspects about4%, and in some aspects about 5%; a minimum percentage of crude fiber inan amount of about 7%, in some aspects about 6%, and in some aspectsabout 5%; a maximum percentage of crude fiber in an amount of about 7%,in some aspects about 6%, and in some aspects about 5%; a minimumpercentage of calcium in an amount of about 0.06%, in some aspects about0.07%, and in some aspects about 0.08%, and a maximum percentage ofcalcium in an amount of about 0.2%, in some aspects about 0.1%, in someaspects about 0.15%, in some aspects about 0.095%, and in some otheraspects about 0.09%; and a minimum percentage of phosphorous in anamount of about 0.7%, in some aspects about 0.75%, and in some otheraspects about 0.8%.

EXAMPLES Example 1

Corn DDGS from a dry grind corn ethanol biorefinery were subjected to ahexane extraction process as described herein to achieve corn distillersmeal having desired nutritional qualities. A selection of thenutritional properties of the corn distillers meal is provided in Table1.

TABLE 1 Nutritional Properties of De-oiled Corn Grain DDGs 06S-05686 AsReceived 100% Dry DDG DE-OILED PLANT TRIAL Basis Matter Basis TotalMoisture, % 4.00 0.000 Total Dry Matter, % 96.0 100 Karl FisherMoisture, % 2.63 Crude Protein, Combustion, % 32.0 33.3 Crude Fat(Diethyl Ether Extract), % 3.03 3.16 Ash, % 4.66 4.85 Crude Fiber,Crucible Method, % 7.06 7.35 Acid Detergent Fiber, % 11.5 12.0 NeutralDetergent Fiber, % 25.6 26.7 Nitrogen Free Extract, % 49.0 51.0Alanine-Total, % 2.26 2.35 Ammonia-Total,% 0.700 0.729 Arginine-Total, %1.24 1.29 Aspartic Acid-Total, % 2.36 2.46 Glutamic Acid-Total, % 5.135.34 Glycine-Total, % 1.17 1.22 Histidine-Total, % 0.704 0.733Isoleucine-Total, % 0.838 0.873 Leucine-Total, % 3.57 3.72 Lysine-Total,% 0.735 0.766 Phenylalanine-Total, % 1.41 1.47 Proline-Total, % 2.502.60 Serine-Total, % 1.58 1.65 Threonine-Total, % 1.13 1.18Tyrosine-Total, % 1.20 1.25 Valine-Total, % 1.21 1.26 TDN (Proximate), %75.7 78.9 NE/Lactation (Proximate), Mcal/lb 0.79 0.82 NE/Maintenance(Proximate), Mcal/lb 0.83 0.86 Metabolizable Energy, kcal/lb 1180 1230NE/Gain (Proximate), Mcal/lb 0.55 0.57

Example 2

Corn DDGS from a dry grind corn ethanol biorefinery were subjected to ahexane extraction process as described herein to achieve corn distillersmeal having desired physical and nutritional properties. A selection ofthe physical and nutritional properties of the corn distillers meal areprovided below in Table 3 and Table 4.

The corn distillers meal was then subjected to two different pelletingprocesses. The pelleting conditions are described below in Table 2, with“Run 1” representing the first pelleting process and “Run 2”representing the second pelleting process. A selection of the physicaland nutritional properties of the pelleted corn distillers meal producedin the two pelleting runs are provided below in Table 3 and Table 4.

TABLE 2 Processing Conditions used for Pelleting Distillers Meal Run 1Run2 Mean St Dev Mean St Dev Pellet Mill CPM #3016 CPM #3016 DieLength/Die 2.25″/ 3/16″ 2.25″/ 3/16″ Diameter Mill discharge temp 170.223.87 172.90 3.32 (° F.) System motor load 39.39 7.81 29.82 1.91 (kW)Throughput (tons/hr) 1.91 0.39 1.13 0.04

TABLE 3 Physical Properties of Distillers Meal and Pelletized DistillersMeal Meal Run 1 Run 2 Property Mean St Dev Mean St Dev Mean St DevMoisture content (%, wb) 10.89 0.25 7.64 0.35 7.52 0.27 Water activity(—) 0.48 0.00 0.36 0.00 0.35 0.00 Particle size - GMD (mm) 0.65 — — — —— Particle size - GSD (mm) 1.87 — — — — — Thermal - conductivity (W/mC)0.08 0.00 — — — — Thermal - diffusivity (mm²/s) 0.12 0.00 — — — —Color - L (—) 45.10 0.99 35.45 0.49 34.62 0.84 Color - a (—) 9.00 0.217.05 0.42 7.03 0.28 Color - b (—) 19.37 0.40 14.05 0.63 13.74 0.46 Fines(%) — — 10.00 3.00 3.00 0.00 Pellet Durability Index (%) — — 61.97 1.8271.98 2.22 Bulk density (lb/ft³) 30.71 0.06 31.96 0.35 35.04 0.12 Angleof repose (°) 14.99 0.51 19.82 1.66 17.87 0.49 Unit density (kg/m³) — —727.17 97.21 605.70 98.64

TABLE 4 Nutritional Properties of Distillers Meal and PelletizedDistillers Meal De-oiled Pellets DDGS Run 1 Run 2 Moisture Content 10.890.25 7.65 0.35 7.52 0.27 (%, wb) Protein (%, db) 34.35 0.07 34.15 0.0733.50 0.14 Fiber (%, db) 8.20 0.14 8.20 0.28 8.00 0.28 Fat (%, db) 2.650.07 4.95 0.07 5.10 0.14 Ash (%, db) 5.01 0.03 4.97 0.09 4.98 0.01Nitrogen Free Extract 49.75 0.21 47.75 0.49 48.45 0.35 (%, db)

Example 3

In the following example, corn distillers meal as described herein wasused as a feed supplement in finishing cattle diets. The performance ofthe diets supplemented with the corn distillers meal was compared to acontrol diet that did not utilized corn distillers meal as a feedsupplement.

Three finishing cattle diets, including a control diet lacking corndistillers meal and two finishing cattle diets including a supplement ofcorn distillers meal, were designed for the study. Substitutions wereiso-nitrogenous where corn distillers meal replaced corn, soy bean mean(“SBM”) and urea. As shown in Table 5, the three diets all contained afixed amount of a liquid supplement formulation including urea, monensinand tylosin, and other micro-ingredients at the same concentration forall three diets. The three diets were: 1) SBM/urea as a control diettypical for feed lots; 2) corn distillers meal replacing SBM and dryurea; and 3) corn distillers meal/SBM where corn distillers mealreplaced 90% of the SBM and the dry urea.

TABLE 5 Diet 2 Diet 3 Corn 10% SBM Diet 1 Distillers 90% Corn SBM MealDistillers Meal Grass Hay % 4.04 4.05 4.05 Whole shelled corn %² 53.7347.45 47.84 High moisture ear corn % 32.33 32.43 32.41 Liquid supplement%² 4.47 4.48 4.48 Pelleted supplement % 5.44 11.59 11.23 SBM³ (5.02) —(1.12) Urea³ (0.42) — — Corn distillers meal³ — (11.59) (10.11) Drymatter (DM) % 74.93 74.84 74.88 Crude protein (CP) % 13.28 13.20 13.24Neutral Detergent Fiber (NDF) %^(a) 14.43 18.40 17.93 Ash %^(a) 2.502.68 2.67 ¹All values except dry matter (DM) on DM basis. ²Contained 45%CP from Urea; 678 g/T monesin; 164 g/T tylosin; fortified with mineralsand vitamins to meet or exceed NRC requirements. ³Values in parenthesesare totaled as Pelleted Supplement. ⁴Treatments differ (P < 0.01)

The cattle had been in the feedlot for more than 60 days prior tobeginning the study. There were 48 steers randomly assigned to each ofthe three diets, 6 steers in 8 pens for each diet. The total number ofsteers was 144. Cattle were fed twice daily in equal proportions overthe course of the 132 day study. All individual steer body weights weremeasured in the morning before feed was delivered. There was no fastingor water deprivation. Step-up diets were used to acclimatize the steersto the study diets and the final diets were first offered on day 22 ofthe study. On day 28 of the study, the steers were implanted withRevalor® S, available from Intervet Inc.

The data for average daily gain (ADG), dry matter intake (DMI), andpounds feed/average daily gain (F/G) were collected and compiled alongwith body weight and feed records. For all interim period reporting,performance calculations were made using unshrunk body weights. Forcumulative performance calculations, final body weight (BW) was shrunkby 3%. The final live body weight of each of the study animals wascalculated as hot carcass weight (HCW) divided by a constant dressingpercentage of 62.5%. On day 132 of the feedlot study, only the morningfeed was delivered and the cattle were harvested the following morning.

Results

The results of this study show that corn distillers meal can be used asa feed supplement and source of CP without any loss of carcass qualityor steer health. More particularly, the study indicates that corndistillers meal may be used as a feed supplement for carbohydrates,protein, as well as non-protein nitrogen (NPN) containing compounds. Asshown by Table 5, the corn distillers meal was used in Diet 2 and Diet 3as a substitute for at least part of the CP from SBM, along withapproximately 0.42% by weight of urea, and approximately 6.5% by weightof dietary corn, relative to the control diet.

Referring to Table 6, steers fed corn distillers meal had significantlyhigher (P<0.05) initial ADG at day 28 and day 56, when compared tosteers fed the control diet. The corn distillers meal diet containedmore neutral detergent fiber than the control diet and digesta retentiontime and water holding may therefore be increased. Diet 2 and Diet 3 hada marginally higher DMI, relative to the control diet. However, as shownin Table 6, the slightly higher DMI did not correspond to significantdifferences in ADG for the study.

With continued reference to Table 6, after day 112, the ADG was verysimilar for each of the diets at each of the testing intervals. Also,the F/G ratio of the de-oiled diets was comparable to the SBM/ureacontrol diet—ranging from approximately 6.67-6.83 pounds on day 112 andfrom approximately 5.91-6.13 pounds on day 132.

TABLE 6 Treatment Diet 1 Diet 2 Diet 3 SBM/ Corn SBM/Com urea DistillersMeal Distillers Meal SEM Initial BW lb 769 769 771 2.0 Day 28 BW lb887^(b)   891^(b)   903^(a)   2.7 ADG lb 4.21^(b) 4.38^(b) 4.71^(a)0.087 DMI lb 17.15^(b) 17.47^(ab) 17.63^(a) 0.118 F/G 4.07^(b) 4.00^(b)3.74^(a) 0.104 Day 56 BW lb 1022 1044 1033 6.1 ADG lb 4.82^(a) 5.44^(b)4.65^(a) 0.195 DMI lb 22.17 23.17 22.70 0.393 F/G 4.62^(ab) 4.26^(a)4.93^(b) 0.166 Day 84 BW lb 1137^(b)    1155^(a)    1147^(b)    4.6 ADGlb 4.12 3.98 4.07 0.132 DMI lb 24.02 24.55 24.11 0.273 F/G 5.84 6.195.97 0.224 Day 112 BW lb 1244^(a)    1264^(b)    1256^(a)    6.3 ADG lb3.82 3.90 3.89 0.143 DMI lb 25.50^(a) 26.51^(b) 25.81^(a) 0.149 F/G 6.766.83 6.67 0.258 Day 132 BW lb 1331 13.50 1339 7.8 ADG lb 4.33 4.31 4.160.216 DMI lb 25.38 2576 25.39 0.420 F/G 5.91 6.10 6.13 0.236 ^(ab)Meanswithout common superscripts differ (P < 0.05)

Tables 7 and 8 show the cumulative data collected during the study andthe carcass traits of the harvested steers. As shown in Table 6, theslightly higher DMI for the corn distillers meal substituted diets didnot correspond to significant differences in diet ADG for the length ofthe study. The cumulative DMI was less than 3% greater for corndistillers meal in contrast to the SBM/urea control diet. As shown inthe bottom half of Table 7, the carcass adjusted final body weight, asderived from the hot carcass weight (HCW), were very similar among thetest diets. The final F/G ratio, carcass adjusted, was 5.83 lbs in theSBM/urea control diet. The F/G ratio in the corn distillers meal dietswas 5.81 lbs and 5.76 lbs. The comparable F/G ratios indicate that thecorn distillers meal substituted diets are just as effective as thecontrol diet for inducing a steadily increasing body weight for thelength of the study. Moreover, as shown in Table 5, the carcass traitsof the corn distillers meal diet were similar to the carcass traits ofthe control diet.

TABLE 7 Treatment Diet 1 Diet 2 Diet 3 SBM/ Corn Distillers SBM/Cornurea Meal Distillers Meal SEM Final BW¹ lb 1291 1310 1299 7.6 ADG lb3.95 4.10 4.00 0.054 DMI lb 22.69 23.35 22.99 0.218 F/G 5.75 5.70 5.750.050 Carcass adjusted Final BW² 1283 1298 1298 7.6 ADG 3.90 4.02 3.990.047 F/G 5.83 5.81 5.76 0.063

TABLE 8 Diet Diet 1 Diet 2 Diet 3 SBM/ Corn Distillers SBM/Corn ureaMeal Distillers Meal SEM Dress %² 62.1 62.0 62.5 0.26 HCW lb 802 812 8124.1 REA in.² 12.49 12.69 12.87 0.182 KPH % 2.35 2.31 2.28 0.037 MarblingScore³ 5.63 5.47 5.78 0.112 Yield Grade 3.33 3.30 3.40 0.069 Choice &Prime % 81.0 79.5 80.2 5.61

Example 4

In the following example, corn DDGS from a dry grind corn ethanolbiorefinery were subjected to a hexane extraction process as describedherein to achieve crude corn oil. More particularly, corn DDGS wereobtained from the removal of ethyl alcohol by distillation from theyeast fermentation of corn by condensing and drying the solids of theresultant whole stillage by methods employed in the grain distillingindustry using the dry milling process. The crude corn oil is furtherremoved from the corn DDGS by hexane extraction for use as food gradecorn oil or for the production of biodiesel and glycerine. A selectionof the nutritional properties of the extracted crude corn oil areprovided in Table 9.

TABLE 9 Oil Extracted From DDGS As Received 100% Basis Dry Matter BasisKarl Fisher Moisture % 1.40 — Crude Protein % 0.560 0.56 Total Nitrogen% 0.0895 0.089 Ash % 0.0800 0.6 Calcium % 0.00800 0.008 Cobolt, ug/g(ppm) — <0.1 Copper, ug/g (ppm) — <2.0 Iron, ug/g (ppm) 14.9 14.9Magnesium % 0.00500 0.005 Molybdenum, ug/g (ppm) — <0.20 Manganese, ug/g(ppm) — <1.0 Phosphorus % 0.0180 0.018 Potassium % 0.00600 0.006 Sodium% 0.00300 0.003 Sulfur % 0.0190 0.019 Zinc, ug/g (ppm) 2.40 2.40 FreeFatty Acids as Oleic % 9.9 9.9

Example 5

Corn DDGS from a dry grind corn ethanol biorefinery were subjected to acommercial grade hexane extraction process as described herein toachieve corn distillers meal having desired nutritional qualities. Aselection of the nutritional properties of the original DDGS and thecorn distillers meal are provided in Table 10.

TABLE 10 Nutritional Properties of Original DDGS and De-Oiled DDGSOrigina DDGS De-Oiled DDGS As Received 100% Dry As Received 100% DryBasis Matter Basis Basis Matter Basis Total Moisture, % 7.57 0.000 4.930.000 Total Dry Matter, % 92.4 100 95.1 100 Karl Fisher Moisture, % 5.803.01 Crude Protein, Combustion, % 27.3 29.5 31.3 32.9 Crude Fat (EtherExtract), % 11.6 12.6 2.53 2.66 Ash, % 4.29 4.64 4.91 5.16 Crude Fiber,% 6.49 7.02 6.23 6.55 Acid Detergent Fiber, % 9.70 10.5 12.0 12.6Neutral Detergent Fiber, % 21.3 23.0 24.6 25.8 Nitrogen Free Extract, %42.7 46.2 50.0 52.6 Total Nitrogen, % 4.37 4.73 5.01 5.27 Calcium, %0.0750 0.0811 0.0940 0.0989 Cobalt, ug/g (ppm) <0.1 <0.1 Copper, ug/g(ppm) 3.70 4.00 5.50 5.79 Iron, ug/g (ppm) 178 193 184 194 Magnesium, %0.355 0.384 0.385 0.405 Manganese, ug/g (ppm) 18.2 19.7 23.3 24.5Molybdenum, ug/g (ppm) 0.66 0.71 0.66 0.69 Phosphorus, % 0.759 0.8210.852 0.896 Potassium, % 0.942 1.02 1.07 1.13 Sodium, % 0.320 0.3460.361 0.380 Sulfur, % 0.772 0.835 0.865 0.910 Zinc, ug/g (ppm) 58.1 62.970.1 73.7 TDN (Proximate), % 79.1 85.6 74.9 78.8

As illustrated by the data provided in Table 10, in general the removalof oil from the corn DDGS such that the corn distillers meal contains acrude fat content less than about 5% increases the concentration of theother nutrients by approximately 10% for the de-oiled DDGS as comparedto the original DDGS.

Example 6

Testing was done using standard Soxhlet apparatus and methodology forsolvent extracting hexane soluble compounds DDGS. A control sample wasinitially run for the purpose of determining the total lipid content ofthe DDGS. In this trial, the standard AOCS method was used except thatn-hexane was used as the solvent instead of the petroleum ether, whichis called for in the AOCS method. Following determination of the totalcontent of the lipids in the DDGS, additional trials were run where thestandard AOCS method was further modified to more accurately representfull scale industrial conditions including, (a) the DDGS was extractedin their natural form (i.e., they were not fine ground into powder), and(b) the extraction time was reduced from 240 minutes to 60 minutes.Reference to “Coarse” in the results summarized Tables 11 and 12 refersto DDGS which was extracted in its natural form (unground). Reference to“Fine” in the results summarized in Tables 11 and 12 refers to DDGSwhich has been finely ground into powder form as called for in the AOCSmethod.

TABLE 11 Nutritional Properties of Original DDGS and De-Oiled DDGSCourse DDGS Fine DDGS As Received De-Oiled As Received De-Oiled TotalMoisture, % (m/m) 11.5% — — — Crude Fat, (hexane extracted) % — 7.79 —9.83 (m/m) Crude Protein, as received % (m/m) — 31.87 29.75 31.14 CrudeProtein, dry matter % (m/m) — 36.01 33.62 35.19 Phosphorus, as received% (m/m) 0.604 0.620 0.594 0.625 Phosphorus, dry matter % (m/m) 0.6820.700 0.671 0.706 Potassium, as received % (m/m) 0.910 0.879 0.874 0.873Potassium, dry matter % (m/m) 1.028 0.994 0.988 0.986 Calcium, asreceived % (m/m) 0.024 0.026 0.023 0.026 Calcium, dry matter % (m/m)0.027 0.029 0.026 0.029 Magnesium, as received % (m/m) 0.315 0.317 0.2930.299 Magnesium, dry matter % (m/m) 0.356 0.358 0.331 0.338 Zinc, asreceived (ppm) 47.134 46.051 44.264 44.949 Zinc, dry matter (ppm) 53.25952.035 50.016 50.790 Manganese, as received (ppm) 15.253 15.334 14.13814.755 Manganese, dry matter (ppm) 17.235 17.327 15.975 16.672 Copper,as received (ppm) 4.037 4.469 4.124 4.307 Copper, dry matter (ppm) 4.5615.050 4.660 4.866 Iron, as received (ppm) 81.254 88.923 95.229 80.817Iron, dry matter (ppm) 91.812 100.478 107.603 91.319 Sodium, as received% 0.158 0.157 0.153 0.159 Sodium, dry matter % 0.179 0.177 0.173 0.180Sulfur, as received % 0.491 0.526 0.485 0.520 Sulfur, dry matter % 0.5550.594 0.548 0.587With respect to the summarized data in Table 11, the components in thedry matter form are restated below with a concentration by hexaneextraction being determined.

TABLE 12 Concentration Extraction-Resulting Percentages ConcentrationCourse DDGS by As Received De-Oiled Extraction Crude Fat, (hexane — 7.79108% extracted) % (m/m) Phosphorus, dry matter 0.682 0.700 103% % (m/m)Potassium, dry matter 1.028 0.994  97% % (m/m) Calcium, dry matter 0.0270.029 107% % (m/m) Magnesium, dry matter 0.356 0.358 101% % (m/m) Zinc,dry matter (ppm) 53.259 52.035 98% Manganese, dry matter 17.235 17.327101% (ppm) Copper, dry matter (ppm) 4.561 5.050 111% Iron, dry matter(ppm) 91.812 100.478 109% Sodium, dry matter % 0.179 0.177  99% Sulfur,dry matter % 0.555 0.594 107%

For the data in Table 12, a concentration factor was calculated, whichrepresents the amount of (lipid) mass removed from the DDGS sample byhexane extraction. By removing oil using a hexane solvent extraction, itis expected that the remaining non-hexane soluble compounds should beconcentrated by approximately 108%. Therefore, if the metal or tracemineral in the DDGS sample is non-soluble in hexane, the concentrationin DDGS should go up by approximately 108% after extraction. As providedin the data summarized in Table 12, the concentration in DDGS went up toabout 108% for calcium, iron, copper and sulfur, which indicates thatthe foregoing compounds are not extracted within the hexane duringhexane solvent extraction of the DDGS.

However if the metal or trace mineral is hexane soluble (i.e., in theform of a hexane soluble compound or complex), then the ratio should notchange and the concentration factor should remain close to approximately100%. As provided in the data summarized in Table 12, the concentrationDDGS remained about 100% for potassium, magnesium, manganese, zinc andsodium, which indicates that the foregoing compounds are extractedwithin the hexane during hexane solvent extraction of the DDGS.

As indicated in the data summarized in Table 12 for phosphorous, theconcentration factor for phosphorous did not remain about 100% nor didit increase to about 108%; instead, the concentration was about 103%.Without wishing to be bound by theory, there may be two or more forms ofphosphorous in DDGS, with one or more inorganic compound(s) orcomplex(es) containing phosphorus and the other being phospholipids,which are known to be soluble in hexane and therefore extracted (i.e.,the 100% concentration factor). This implies that the remainingphosphorous compound(s) or complex(s) in DDGS must be inorganiccompound(s) or complex(es) containing phosphorous (i.e., the 108%concentration factor). Thus, at least a portion of the phosphorousand/or phosphorous containing compound(s) or complex(s) are extractedwithin the hexane during hexane solvent extraction of the DDGS.

Since only a portion of the phosphorous and/or phosphorous containingcompound(s) or complex(s) are extracted within the hexane during hexanesolvent extraction of the DDGS, the extracted oil with a reducedphosphorous content may be used in the hydrotreating process to producea diesel fuel without necessarily requiring additional treatment of theextracted oil to address the phosphorous content.

Example 7

Testing was done on the oil extraction of DDGS relating to coarse DDGSand fine DDGS. In this trial, oil in the DDGS was solvent extractedusing commercial grade hexane. Samples of the coarse DDGS and fine DDGSwere analyzed at intervals of 15 minutes, 30 minutes, 60 minutes, and 90minutes. Reference to “Coarse” in the results summarized in Table 13refers to DDGS which was extracted in its natural form (unground), whichparticle size distribution by weight and size are provided in Tables 14and 15. Reference to “Fine” in the results summarized in Table 13 refersto DDGS that finely ground into powder form and all passed thru a 1 mmscreen as called for in the AOCS Soxhlet method, which particle sizedistribution by weight and size are provided in Tables 14 and 15. Theoil content of the coarse DDGS sample had a starting oil content ofabout 9.53% while the fine DDGS had a starting oil content of about10.65% by weight.

TABLE 13 DDGS Particle Size on Oil Extraction Coarse DDGS Fine DDGSTime, min. % oil extracted % residual oil % oil extracted % residual oil 0 — 9.53 — 10.65 15 66.3 3.59 94.8 0.56 30 68.8 3.32 95.0 0.53 60 72.92.89 95.7 0.46 90 70.5 3.14 96.3 0.39

TABLE 14 DDGS Particle Size-Weight Percentage U.S. Coarse DDGS Fine DDGSSieve No. (% Retained) (% Retained)  6 0.2 0.0  8 0.4 0.0  12 1.2 0.0 16 11.5 0.0  20 26.6 0.0  30 51.4 13.1  40 45.0 14.7  50 7.6 0.4  7015.1 2.5 100 5.1 1.0 140 2.1 0.1 200 0.3 0.0 270 0.0 0.0 Pan 0.0 0.0Average 591.20 521.35 Particle Size (microns)

TABLE 15 DDGS Particle Size-Quantity Percentage U.S. Coarse DDGS FineDDGS Sieve No. (% Retained) (% Retained)  6 0.13 0.0  8 0.22 0.0  120.73 0.0  16 6.90 0.0  20 16.02 0.13  30 30.88 41.24  40 27.02 26.26  504.58 1.20  70 9.06 7.95 100 3.05 3.03 140 1.26 0.19 200 0.16 0.0 270 0.00.0 Pan 0.0 0.0 TOTAL 100 100 Average 591.20 521.35 Particle Size(microns)As provided in the data summarized in Table 13, coarse DDGS that isprovided in its natural form (i.e., unground), resulted in a residualoil content of about 3% after 90 minutes. In contrast, the DDGS that wasall ground to a particle size less than about 1 mm resulted in aresidual oil content of about 0.39% after 90 minutes. Similarly, thepercentage of oil extracted from DDGS using solvent extraction increasedas the particle size of the DDGS was reduced.

It should be emphasized that the described embodiments of thisdisclosure are merely possible examples of implementations and are setforth for a clear understanding of the principles of this disclosure.Many variations and modifications may be made to the describedembodiments of this disclosure without departing substantially from thespirit and principles of this disclosure. All such modifications andvariations are intended to be included herein within the scope of thisdisclosure and protected by the following claims.

The invention claimed is:
 1. An oleochemical processed from crude cornoil that is extracted from corn distillers dried grains and/or corndistillers dried grain soluble using a solvent extraction process, thecrude corn oil comprising: free fatty acids in an amount ranging fromabout 1% to about 15% by weight of the crude corn oil, wherein theoleochemical processed from the crude corn oil is substantially freefrom non-native emulsifiers and flocculants.
 2. The oleochemical ofclaim 1 processed by fat splitting at least a portion of glycerides fromthe crude corn oil into a crude fatty acid portion and a crude glycerineportion, wherein the crude fatty acid portion or the crude glycerineportion is processed into the oleochemical.
 3. The oleochemical of claim2, wherein the oleochemical is used as an industrial manufacturingoleochemical, a personal care product oleochemical, or a home careproduct oleochemical.
 4. The oleochemical processed from crude corn oilof claim 1, wherein the crude corn oil comprising phosphorous in anamount no more than about 0.05%.